Compositions containing an etheramine

ABSTRACT

The present disclosure relates generally to cleaning compositions and, more specifically, to cleaning compositions containing an etheramine that is suitable for removal of stains from soiled materials.

JOINT RESEARCH AGREEMENT

The inventions described and claimed herein were made pursuant to aJoint Research Agreement between The Procter & Gamble Company and BASFSE of Ludwigshafen, Germany.

TECHNICAL FIELD

The present disclosure relates generally to cleaning compositions and,more specifically, to cleaning compositions containing an etheraminethat is suitable for removal of stains from soiled materials.

BACKGROUND

Due to the increasing popularity of easy-care fabrics made of syntheticfibers as well as the ever increasing energy costs and growingecological concerns of detergent users, the once popular warm and hotwater washes have now taken a back seat to washing fabrics in cold water(30° C. and below). Many commercially available laundry detergents areeven advertised as being suitable for washing fabrics at 15° C. or even9° C. To achieve satisfactory washing results at such low temperatures,results comparable to those obtained with hot-water washes, the demandson low-temperature detergents are especially high.

It is known to include certain additives in detergent compositions toenhance the detergent power of conventional surfactants, so as toimprove the removal of grease stains at temperatures of 30° C. andbelow. For example, laundry detergents containing an aliphatic aminecompound, in addition to at least one synthetic anionic and/or nonionicsurfactant, are known. Also, the use of linear, alkyl-modified(secondary) alkoxypropylamines in laundry detergents to improve cleaningat low temperatures is known. These known laundry detergents, however,are unable to achieve satisfactory cleaning at cold temperatures.

Furthermore, the use of linear, primary polyoxyalkyleneamines (e.g.,Jeffamine® D-230) to stabilize fragrances in laundry detergents andprovide longer lasting scent is also known. Also, the use ofhigh-molecular-weight (molecular weight of at least about 1000),branched, trifunctional, primary amines (e.g., Jeffamine® T-5000etheramine) to suppress suds in liquid detergents is known.Additionally, an etheramine mixture containing a monoether diamine(e.g., at least 10% by weight of the etheramine mixture), methods forits production, and its use as a curing agent or as a raw material inthe synthesis of polymers are known. Finally, the use of compoundsderived from the reaction of diamines or polyamines with alkylene oxidesand compounds derived from the reaction of amine terminated polyetherswith epoxide functional compounds to suppress suds is known.

Also, cleaning compositions comprising a surfactant system and apolyetheramine of Formula (I), Formula (II), or a mixture thereof:

where each of R₁-R₁₂ is independently selected from H, alkyl,cycloalkyl, aryl, alkylaryl, or arylalkyl, where at least one of R₁-R₆and at least one of R₇-R₁₂ is different from H, each of A₁-A₉ isindependently selected from linear or branched alkylenes having 2 to 18carbon atoms, each of Z₁-Z₄ is independently selected from OH or NH₂,where at least one of Z₁-Z₂ and at least one of Z₃-Z₄ is NH₂, where thesum of x+y is in the range of about 2 to about 200, where x≥1 and y≥1,and the sum of x₁+y₁ is in the range of about 2 to about 200, where x₁≥1and y₁≥1, are known. These cleaning compositions can provide increasedgrease removal, particularly in cold water, e.g., at 30° C. or evenlower.

While cleaning compositions that comprise etheramine(s) and provideincreased grease removal (particularly in cold water) are known. Thereis a continuing need for a material that not only removes grease, butreduces redeposition of the grease on the target substrate, such asfabric. The compositions of the present disclosure provide surprisinglyeffective grease removal and antiredeposition benefits.

SUMMARY

The present disclosure relates to method of forming an etheramine. Themethod comprising reductive cyanoethylation of an alkoxylated 1,3-diolmixture with an acrylonitrile in the presence of a base followed byhydrogentation with hydrogen and a catalyst to form an etheramine ofFormula (I), Formula (II), or a mixture thereof:

where each of R₁-R₁₂ is independently selected from H, alkyl,cycloalkyl, aryl, alkylaryl, or arylalkyl, where at least one of R₁-R₆and at least one of R₇-R₁₂ is different from H, each of A₁-A₉ isindependently selected from linear or branched alkanediyl groups having2 to 18 carbon atoms, each of Z₁-Z₄ is independently selected from —OHor linear —OCH₂CH₂CH₂NH₂, where the degree of amination of each of theetheramines of Formula (I) and Formula (H) is equal to or greater thanabout 50%, where the sum of x+y is in the range of about 2 to about 200,where x≥1 and y≥1, and the sum of x₁+y₁ is in the range of about 2 toabout 200, where x₁≥1 and y₁≥1.

DETAILED DESCRIPTION

Features and benefits of the present invention will become apparent fromthe following description, which includes examples intended to give abroad representation of the invention. Various modifications will beapparent to those skilled in the art from this description and frompractice of the invention. The scope is not intended to be limited tothe particular forms disclosed and the invention covers allmodifications, equivalents, and alternatives falling within the spiritand scope of the invention as defined by the claims.

As used herein, the articles including “the,” “a” and “an” when used ina claim or in the specification, are understood to mean one or more ofwhat is claimed or described.

As used herein, the terms “include,” “includes” and “including” aremeant to be non-limiting.

The term “substantially free of” or “substantially free from” as usedherein refers to either the complete absence of an ingredient or aminimal amount thereof merely as impurity or unintended byproduct ofanother ingredient. A composition that is “substantially free” of/from acomponent means that the composition comprises less than about 0.5%,0.25%, 0.1%, 0.05%, or 0.01%, or even 0%, by weight of the composition,of the component.

As used herein the phrases “detergent composition” and “cleaningcomposition” are used interchangeably and include compositions andformulations designed for cleaning soiled material. Such compositionsinclude but are not limited to, laundry cleaning compositions anddetergents, fabric softening compositions, fabric enhancingcompositions, fabric freshening compositions, laundry prewash, laundrypretreat, laundry additives, spray products, dry cleaning agent orcomposition, laundry rinse additive, wash additive, post-rinse fabrictreatment, ironing aid, dish washing compositions, hard surface cleaningcompositions, unit dose formulation, delayed delivery formulation,detergent contained on or in a porous substrate or nonwoven sheet, andother suitable forms that may be apparent to one skilled in the art inview of the teachings herein. Such compositions may be used as apre-laundering treatment, a post-laundering treatment, or may be addedduring the rinse or wash cycle of the laundering operation.

The term “etheramine” includes the term “polyetheramine” and includesamines that have one or more ether groups.

The term “linear” refers to a straight chain, non-branched hydrocarbon.

It should be understood that every maximum numerical limitation giventhroughout this specification includes every lower numerical limitation,as if such lower numerical limitations were expressly written herein.Every minimum numerical limitation given throughout this specificationwill include every higher numerical limitation, as if such highernumerical limitations were expressly written herein. Every numericalrange given throughout this specification will include every narrowernumerical range that falls within such broader numerical range, as ifsuch narrower numerical ranges were all expressly written herein.

All cited patents and other documents are, in relevant part,incorporated by reference as if fully restated herein. The citation ofany patent or other document is not an admission that the cited patentor other document is prior art with respect to the present invention.

In this description, all concentrations and ratios are on a weight basisof the detergent composition unless otherwise specified.

Composition

The compositions of the present disclosure may be detergentcompositions, more specifically laundry detergent compositions. Thecompositions may have a form selected from liquid, powder, single-phaseor multi-phase unit dose, pouch, tablet, gel, paste, bar, flake. Thecompositions may have a form selected from the group consisting of aliquid laundry detergent, a gel detergent, a single-phase or multi-phaseunit dose detergent, a detergent contained in a single-phase ormulti-phase or multi-compartment water-soluble pouch, a liquid handdishwashing composition, a laundry pretreat product, a fabric softenercomposition, and mixtures thereof.

The term “liquid” encompasses aqueous compositions, non-aqueouscompositions, gels, pastes, dispersions and the like. The phrase“laundry detergent composition,” as used herein, means a compositionthat can be used in a laundry wash and/or rinse operation. A laundrydetergent composition can also be a laundry pre-treatment composition.The composition may be a liquid laundry detergent composition that ispresent in a water-soluble unit dose article.

The compositions of the present disclosure may be detergent compositionsand may comprise an etheramine. Suitable etheramines are described inmore detail below.

Etheramines

The compositions disclosed herein may comprise an etheramine. Thecompositions may comprise from about 0.1% to about 10%, or from about0.2% to about 5%, or from about 0.5% to about 3%, by weight of thecomposition, of an etheramine of Formula (I), Formula (II), or a mixturethereof:

where each of R₁-R₁₂ is independently selected from H, alkyl,cycloalkyl, aryl, alkylaryl, or arylalkyl, where at least one of R₁-R₆and at least one of R₇-R₁₂ is different from H, each of A₁-A₉ isindependently selected from linear or branched alkylenes having 2 to 18carbon atoms, each of Z₁-Z₄ is independently selected from —OH or linear—OCH₂CH₂CH₂NH₂, where the degree of amination of each of the etheraminesof Formula (I) and Formula (II) is equal to or greater than about 50%,where the sum of x+y is in the range of about 2 to about 200, about 2 toabout 20, about 3 to about 20, about 2 to about 10, about 2 to about 8,about 3 to about 8, or about 4 to about 6, where x≥1 and y≥1, and thesum of x₁+y₁ is in the range of about 2 to about 200, about 2 to about20, about 3 to about 20, about 2 to about 10, about 2 to about 8, about3 to about 8, about 4 to about 6, or about 2 to about 4, where x₁≥1 andy₁≥1.

The etheramine of Formula (I), Formula (II), or a mixture thereof mayhave equal to or greater than 50% of the Z₁-Z₄ groups being linear1-oxy-3-propyl-amine groups (—OCH₂CH₂CH₂NH₂). Without being bound bytheory, it is believed that such etheramines of Formula (I) and Formula(II), where the degree of amination is equal to or greater than 50%,provide improved grease removal and antiredeposition benefits.

In Formula (I) or (II), each of A₁-A₉ is independently selected fromethylene, propylene, or butylene. Each of A₁-A₉ may be propylene. InFormula (I) or (II), R₁, R₂, R₅, R₆, R₇, R₈, R₁₁, and R₁₂ may each be H,and each of R₃, R₄, R₉, and R₁₀ may be independently selected from C₁₋₁₆alkyl or aryl. Each of R₁, R₂, R₅, R₆, R₇, R₈, R₁₁, and R₁₂ may be H andeach of R₃, R₄, R₉, and R₁₀ may be independently selected from a butylgroup, an ethyl group, a methyl group, a propyl group, or a phenylgroup. In Formula (I) or (II), R₃ and R₉ may each be an ethyl group, andeach of R₁, R₂, R₅, R₆, R₇, R₈, R₁₁, and R₁₂ may be each H, and/or R₄and R₁₀ may each be a butyl group. Each of R₁, R₂, R₇, and R₈ may be Hand each of R₃, R₄, R₅, R₆, R₉, R₁₀, R₁₁, and R₁₂ may be independentlyselected from an ethyl group, a methyl group, a propyl group, a butylgroup, a phenyl group, or H.

In Formula (I), each of x, x₁, y, and/or y₁ may independently be equalto 3 or greater, meaning that the etheramine of Formula (I) may havemore than one [A₂—O] group, more than one [A₃—O] group, more than one[A₄—O] group, and/or more than one [A₅—O] group. A₂ may be selected fromethylene, propylene, butylene, or mixtures thereof. A₃ may be selectedfrom ethylene, propylene, butylene, or mixtures thereof. A₄ may beselected from ethylene, propylene, butylene, or mixtures thereof. A_(s)may be selected from ethylene, propylene, butylene, or mixtures thereof.Similarly, the etheramine of Formula (II) may have more than one [A₇—O]group and/or more than one [A₈—O] group. A₇ may be selected fromethylene, propylene, butylene, or mixtures thereof. A₈ may be selectedfrom ethylene, propylene, butylene, or mixtures thereof.

In other words, [A₂—O] may be selected from ethylene oxide, propyleneoxide, butylene oxide, or mixtures thereof. [A₃—O] may be selected fromethylene oxide, propylene oxide, butylene oxide, or mixtures thereof.[A₄—O] may be selected from ethylene oxide, propylene oxide, butyleneoxide, or mixtures thereof. [A₅—O] may be selected from ethylene oxide,propylene oxide, butylene oxide, or mixtures thereof. [A₇—O] may beselected from ethylene oxide, propylene oxide, butylene oxide, ormixtures thereof. [A₈—O] may be selected from ethylene oxide, propyleneoxide, butylene oxide, or mixtures thereof.

When A₂, A₃, A₄, and/or A_(s) are mixtures of ethylene, propylene,and/or butylenes, the resulting alkoxylate may have a block-wisestructure or a random structure. When A₇ and/or A₈ are mixtures ofethylene, propylene, and/or butylenes, the resulting alkoxylate may havea block-wise structure or a random structure. For a non-limitingillustration, when x=7 in the etheramine of Formula (I), then theetheramine comprises six [A₄—O] groups. If A₄ comprises a mixture ofethylene groups and propylene groups, then the resulting etheraminewould comprise a mixture of ethoxy (EO) groups and propoxy (PO) groups.These groups may be arranged in a random structure (e.g.,EO-EO-PO-EO-PO-PO) or a block-wise structure (EO-EO-EO-PO-PO-PO). Inthis illustrative example, there are an equal number of different alkoxygroups (here, three EO and three PO), but there may also be differentnumbers of each alkoxy group (e.g., five EO and one PO). Furthermore,when the etheramine comprises alkoxy groups in a block-wise structure,the etheramine may comprise two blocks, as shown in the illustrativeexample (where the three EO groups form one block and the three POgroups form another block), or the etheramine may comprise more than twoblocks. The above discussion also applies to etheramines according toFormula (II).

The etheramine may comprise a mixture of the compound of Formula (I) andthe compound of Formula (II).

The etheramine of Formula (I) or Formula (I) may have a weight averagemolecular weight of about 290 to about 1000 grams/mole, about 290 toabout 900 grams/mole, about 300 to about 700 grams/mole, or about 300 toabout 450 grams/mole. The molecular mass of a polymer differs fromtypical molecules in that polymerization reactions produce adistribution of molecular weights, which is summarized by the weightaverage molecular weight. The etheramine polymers of the invention arethus distributed over a range of molecular weights. Differences in themolecular weights are primarily attributable to differences in thenumber of monomer units that sequence together during synthesis. Withregard to the etheramine polymers of the invention, the monomer unitsare the alkylene oxides that react with the 1,3-diols of formula (III)to form alkoxylated 1,3-diols, which are then reductively cyanoethylatedto form the resulting etheramine polymers. The resulting etheraminepolymers are characterized by the sequence of alkylene oxide units. Thealkoxylation reaction results in a distribution of sequences of alkyleneoxide and, hence, a distribution of molecular weights. The alkoxylationreaction also produces unreacted alkylene oxide monomer (“unreactedmonomers”) that do not react during the reaction and remain in thecomposition.

The etheramine may comprise an etheramine mixture comprising at least90%, by weight of the etheramine mixture, of the etheramine of Formula(I), the etheramine of Formula(II), or a mixture thereof. The etheraminemay comprise an etheramine mixture comprising at least 95%, by weight ofthe etheramine mixture, of the etheramine of Formula (I), the etheramineof Formula(II), or a mixture thereof.

The etheramine of Formula (I) and/or the etheramine of Formula(II) maybe obtainable by: a) reacting a 1,3-diol of formula (III) with C₂-C₁₈alkylene oxide to form alkoxylated 1,3-diols, wherein the molar ratio of1,3-diol to C₂-C₁₈ alkylene oxide is in the range of about 1:2 to about1:10,

where R₁-R₆ are independently selected from H, alkyl, cycloalkyl, aryl,alkylaryl, or arylalkyl, where at least one of R₁-R₆ is different fromH;b) reductive cyanoethylation of the alkoxylated 1,3-diols.

Generally, as used herein, the term “obtainable by” means thatcorresponding products do not necessarily have to be produced (i.e.obtained) by the corresponding method or process de-scribed in therespective specific context, but also products are comprised whichexhibit all features of a product produced (obtained) by saidcorresponding method or process, wherein said products were actually notproduced (obtained) by such method or process. However, the term“obtainable by” also comprises the more limiting term “obtained by”,i.e. products which were actually produced (obtained) by a method orprocess described in the respective specific context.

The molar ratio of 1,3-diol to C₂-C₁₈ alkylene oxide may be in the rangeof about 1:1 to about 1:8, about 1:2 to about 1:10, about 1:2 to about1:7, about 1:3 to about 1:6, or about 1:4 to about 1:5. The C₂-C₁₈alkylene oxide may be selected from ethylene oxide, propylene oxide,butylene oxide or a mixture thereof. The C₂-C₁₈ alkylene oxide may bepropylene oxide.

In the 1,3-diol of formula (III), R₁, R₂, R₅, and R₆ may be H and R₃ andR₄ may be C₁₋₁₆ alkyl or aryl. The 1,3-diol of formula (III) may beselected from 2-butyl-2-ethyl-1,3-propanediol,2-methyl-2-propyl-1,3-propanediol, 2-methyl-2-phenyl-1,3-propanediol,2,2-dimethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, or a mixturethereof.

Step a): Alkoxylation

The 1,3-diols of Formula III may be synthesized as described inWO10026030, WO10026066, WO09138387, WO09153193, and WO10010075. Suitable1,3-diols include 2,2-dimethyl-1,3-propane diol,2-butyl-2-ethyl-1,3-propane diol, 2-pentyl-2-propyl-1,3-propane diol,2-(2-methyl)butyl-2-propyl-1,3-propane diol, 2,2,4-trimethyl-1,3-propanediol, 2,2-diethyl-1,3-propane diol, 2-methyl-2-propyl-1,3-propane diol,2-ethyl-1,3-hexane diol, 2-phenyl-2-methyl-1,3-propane diol,2-methyl-1,3-propane diol, 2-ethyl-2-methyl-1,3 propane diol,2,2-dibutyl-1,3-propane diol, 2,2-di(2-methylpropyl)-1,3-propane diol,2-isopropyl-2-methyl-1,3-propane diol, or a mixture thereof. The1,3-diol may be selected from 2-butyl-2-ethyl-1,3-propanediol,2-methyl-2-propyl-1,3-propanediol, 2-methyl-2-phenyl-1,3-propanediol, ora mixture thereof.

An alkoxylated 1,3-diol may be obtained by reacting a 1,3-diol ofFormula II with an alkylene oxide, according to any number of generalalkoxylation procedures known in the art. Suitable alkylene oxidesinclude C₂-C₁₈ alkylene oxides, such as ethylene oxide, propylene oxide,butylene oxide, pentene oxide, hexene oxide, decene oxide, dodeceneoxide, or a mixture thereof. The C₂-C₁₈ alkylene oxide may be selectedfrom ethylene oxide, propylene oxide, butylene oxide, or a mixturethereof. A 1,3-diol may be reacted with a single type of alkylene oxideor combinations of two or more different types of alkylene oxides. Whenusing two or more different types of alkylene oxides, the resultingpolymer may be obtained as a block-wise structure or a random structure.

The molar ratio of 1,3-diol to C₂-C₁₈ alkylene oxide at which thealkoxylation reaction is carried out may be in the range of about 1:2 toabout 1:10, or about 1:3 to about 1:8, or about 1:4 to about 1:6.

The alkoxylation reaction generally proceeds in the presence of acatalyst in an aqueous solution at a reaction temperature of from about70° C. to about 200° C. or from about 80° C. to about 160° C. Thereaction may proceed at a pressure of up to about 10 bar or up to about8 bar. Examples of suitable catalysts include basic catalysts, such asalkali metal and alkaline earth metal hydroxides, e.g., sodiumhydroxide, potassium hydroxide and calcium hydroxide, alkali metalalkoxides, in particular sodium and potassium C₁-C₄-alkoxides, e.g.,sodium methoxide, sodium ethoxide and potassium tert-butoxide, alkalimetal and alkaline earth metal hydrides, such as sodium hydride andcalcium hydride, and alkali metal carbonates, such as sodium carbonateand potassium carbonate. The catalyst may be an alkali metal hydroxide,such as potassium hydroxide or sodium hydroxide. Typical use amounts forthe catalyst are from about 0.05 to about 10% by weight, or from about0.1 to about 2% by weight, based on the total amount of 1,3-diol andalkylene oxide. During the alkoxylation reaction, certainimpurities—unintended constituents of the polymer—may be formed, such ascatalysts residues.

Alkoxylation with x+y+x₁+y₁−2 C₂-C₁₈ alkylene oxides produces structuresas represented by Formula IV and/or Formula V:

where R₁-R₁₂ are independently selected from H, alkyl, cycloalkyl, aryl,alkylaryl, or arylalkyl, where at least one of R₁-R₆ and at least one ofR₇-R₁₂ is different from H, each of A₁-A₉ is independently selected fromlinear or branched alkanediyl groups having 2 to 18 carbon atoms, or 2to 10 carbon atoms, or 2 to 5 carbon atoms, and the sum of x+y is in therange of about 2 to about 200, or about 2 to about 20, or about 3 toabout 20, or about 2 to about 10, or about 2 to about 8, or about 2 toabout 5, where x≥1 and y≥1, and the sum of x₁+y₁ is in the range ofabout 2 to about 200, or about 2 to about 20, or about 3 to about 20, orabout 2 to about 10, or about 2 to about 8, or about 2 to about 5, wherex₁≥1 and y₁≥1.

Step b): Amination

Amination of the alkoxylated 1,3-diols may be carried out by reductivecyanoethylation, and produces structures represented by Formula I and/orFormula II:

where each of R₁-R₁₂ is independently selected from H, alkyl,cycloalkyl, aryl, alkylaryl, or arylalkyl, where at least one of R₁-R₆and at least one of R₇-R₁₂ is different from H, each of A₁-A₉ isindependently selected from linear or branched alkanediyl groups having2 to 18 carbon atoms, or 2 to 10 carbon atoms, or 2 to 5 carbon atoms,where each of Z₁-Z₄ is independently selected from —OH or linear—OCH₂CH₂CH₂NH₂, where the degree of amination of each of the etheraminesof Formula (I) and Formula (II) is equal to or greater than 50%, wherethe sum of x+y is in the range of about 2 to about 200, or about 2 toabout 20, or about 3 to about 20, or about 2 to about 10, or about 2 toabout 8, or about 2 to about 5, where x≥1 and y≥1, and the sum of x, +y,is in the range of about 2 to about 200, or about 2 to about 20, orabout 3 to about 20, or about 2 to about 10, or about 2 to about 8, orabout 2 to about 5, where x₁≥1 and y₁≥1.

Etheramines according to Formula I and/or Formula II may be obtained byreductive cyanoethylation of the alkoxylated 1,3-diol mixture (FormulaIV and V). The reductive cyanoethylation may be carried out by reactionof the alkoxylated 1,3-diol mixture (Formula IV and V) withacrylonitrile in the presence of a base followed by hydrogenation withhydrogen and a catalyst. The use of acrylonitrile produces linearoxypropylamine end groups according to the present disclosure.

Suitable bases include alkaline hydroxides and substituted ammoniumhydroxide. Tetrakis(2-hydroxyethyl)ammonium hydroxide may be used as abase.

As catalysts for hydrogenation of the nitrile function to thecorresponding amine, catalysts which comprise one or more elements ofthe 8th transition group of the Periodic Table (Fe, Co, Ni, Ru, Rh, Pd,Os, Ir, Pt), or Fe, Co, Ni, Ru or Rh, or Co or Ni may be used. Catalystswhich comprise Co, as an active component, may be used. Another suitableactive component is Cu.

The abovementioned catalysts can be doped in a known way with promoters,for example, chromium, iron, cobalt, manganese, molybdenum, titanium,tin, metals of the alkali metal group, metals of the alkaline earthmetal group, and/or phosphorus.

The catalyst may be a skeletal catalyst (also referred to as Raney®type, hereinafter also: Raney catalyst) that is obtained by leaching(activating) an alloy of hydrogenation-active metal and a furthercomponent (e.g., Al). Suitably catalysts include Raney nickel catalystsand Raney cobalt catalysts.

Supported Pd or Pt catalysts may also be used as catalysts. Suitablesupport materials include activated carbon, Al₂O₃, TiO₂, ZrO₂ and SiO₂.The catalyst may be produced by reduction of catalyst precursors.

The catalyst precursor may comprise an active composition that comprisesone or more catalytically active components, optionally promoters, andoptionally a support material.

The catalytically active components comprise oxygen-comprising compoundsof the above-mentioned metals, for example the metal oxides orhydroxides thereof, e.g., CoO, NiO, CuO and/or mixed oxides thereof.

As used herein, the term “catalytically active components” refers to theabovementioned oxygen-comprising metal compounds but is not intended tomean that these oxygen-comprising compounds are themselves catalyticallyactive. The catalytically active components generally display catalyticactivity in the reaction according to the disclosure only afterreduction.

Suitable catalyst precursors include the oxide mixtures which aredisclosed in EP-A-0636409 and before reduction with hydrogen comprisefrom 55 to 98% by weight of Co, calculated as CoO, from 0.2 to 15% byweight of phosphorus, calculated as H₃PO₄, from 0.2 to 15% by weight ofmanganese, calculated as MnO₂, and from 0.2 to 5.0% by weight of alkalimetal, calculated as M₂O (M=alkali metal), or oxide mixtures which aredisclosed in EP-A-0742045 and before reduction with hydrogen comprisefrom 55 to 98% by weight of Co, calculated as CoO, from 0.2 to 15% byweight of phosphorus, calculated as H₃PO₄, from 0.2 to 15% by weight ofmanganese, calculated as MnO₂, and from 0.05 to 5% by weight of alkalimetal, calculated as M₂O (M=alkali metal), or oxide mixtures which aredisclosed in EP-A-696572 and before reduction with hydrogen comprisefrom 20 to 85% by weight of ZrO₂, from 1 to 30% by weight ofoxygen-comprising compounds of copper, calculated as CuO, from 30 to 70%by weight of oxygen-comprising compounds of nickel, calculated as NiO,from 0.1 to 5% by weight of oxygen-comprising compounds of molybdenum,calculated as MoO₃, and from 0 to 10% by weight of oxygen-comprisingcompounds of aluminum and/or manganese, calculated as Al₂O₃ or MnO₂, forexample the composition having 31.5% by weight of ZrO₂, 50% by weight ofNiO, 17% by weight of CuO and 1.5% by weight of MoO₃, or oxide mixtureswhich are disclosed in EP-A-963 975 and before reduction with hydrogencomprise from 22 to 40% by weight of ZrO₂, from 1 to 30% by weight ofoxygen-comprising compounds of copper, calculated as CuO, from 15 to 50%by weight of oxygen-comprising compounds of nickel, calculated as NiO,with the molar ratio of Ni:Cu being greater than 1, from 15 to 50% byweight of oxygen-comprising compounds of cobalt, calculated as CoO, from0 to 10% by weight of oxygen-comprising compounds of aluminum and/ormanganese, calculated as Al₂O₃ or MnO₂, and no oxygen-comprisingcompounds of molybdenum, for example, the catalyst having thecomposition 33% by weight of Zr, calculated as ZrO₂, 28% by weight ofNi, calculated as NiO, 11% by weight of Cu, calculated as CuO, and 28%by weight of Co, calculated as CoO.

The process can be carried out in a continuous or discontinuous mode,e.g., in an autoclave, tube reactor or fixed-bed reactor. The reactordesign is also not narrowly critical. The feed thereto may be upflowingor downflowing, and design features in the reactor which optimize plugflow in the reactor may be employed.

The degree of amination may be equal to or greater than about 50%, orequal to or greater than about 55%, or in the range of from about 60% toabout 95%, or from about 65% to about 90%, or from about 70% to about85%. The degree of amination may be calculated from the total aminevalue (AZ) divided by sum of the total acetylables value (AC) andtertiary amine value (tert. AZ) multiplied by 100: (Total AZ: (AC+tert.AZ))×100). The total amine value (AZ) is determined according to DIN16945. The total acetylables value (AC) is determined according to DIN53240. The secondary and tertiary amine are determined according to ASTMD2074-07.

The primary amines value may be calculated as follows: primary aminevalue=AZ−secondary+tertiary amine value. Primary amine in % of totalamine is calculated as follows: Primary amine in%=((AZ−secondary+tertiary amine value)/AZ)*100. The degree of aminationis calculated from (total acetylables value−hydroxyl value)/totalacetylables value.

The hydroxyl value is calculated from (total acetylables value+tertiaryamine value)−total amine value.

The etheramines of the disclosure are effective for removal of stains,particularly grease, and the etheramines reduce redeposition of thegrease on the target substrate, such as fabric. Also, cleaningcompositions containing the etheramines of the disclosure do not exhibitthe cleaning negatives seen with some conventional amine-containingcleaning compositions on hydrophilic bleachable stains, such as coffee,tea, wine, or particulates. Additionally, unlike some conventionalamine-containing cleaning compositions, the etheramines of thedisclosure do not contribute to whiteness negatives on white fabrics.

A further advantage of cleaning compositions containing the etheraminesof the invention is their ability to remove grease stains in cold water,for example, via pretreatment of a grease stain followed by cold waterwashing. Without being limited by theory, it is believed that cold waterwashing solutions have the effect of hardening or solidifying grease,making the grease more resistant to removal, especially on fabric.Cleaning compositions containing the etheramines of the invention aresurprisingly effective when used as part of a pretreatment regimenfollowed by cold water washing.

The etheramines of the invention may be used in the form of awater-based, water-containing, or water-free solution, emulsion, gel orpaste of the etheramine together with an acid such as, for example,citric acid, lactic acid, sulfuric acid, methanesulfonic acid, hydrogenchloride, e.g., aqeuous hydrogen chloride, phosphoric acid, formic acid,acetic acid, propionic acid, valeric acid, oxalic acid, succinic acid,adipic acid, sebacic acid, glutaric acid, glucaric acid, tartaric acid,malic acid, benzoic acid, salicylic acid, phthalic acid, oleic acid,stearic acid, caproic acid, caprylic acid, capric acid, lauric acid,myristic acid, palmitic acid, linoleic acid or mixtures thereof. Theacid may be selected from the group consisting of caproic acid, caprylicacid, capric acid, lauric acid, myristic acid, and mixtures thereof.Alternatively, the acid may be represented by a surfactant, such as,alkyl benzene sulphonic acid, alkylsulphonic acid, monoalkyl esters ofsulphuric acid, mono alkylethoxy esters of sulphuric acid, fatty acids,alkyl ethoxy carboxylic acids, and the like, or mixtures thereof. Whenapplicable or measurable, the preferred pH of the solution or emulsionranges from pH 3 to pH 11, or from pH 6 to pH 9.5, even more preferredfrom pH 7 to pH 8.5.

Surfactant

The compositions disclosed herein may comprise a surfactant selectedfrom the group consisting of anionic surfactants, nonionic surfactants,cationic surfactants, zwitterionic surfactants, amphoteric surfactants,ampholytic surfactants, and mixtures thereof.

Anionic Surfactant

The compositions of the present disclosure may comprise at least about10%, or at least about 20%, or at least about 30%, or at least about50%, or at least about 60%, or at least about 70% by weight of ananionic surfactant. The compositions of the present disclosure maycomprise less than 100%, or less than 90%, or less than about 85%, orless than about 75%, or less than about 70% by weight of an anionicsurfactant. The compositions of the present disclosure may comprise fromabout 10% to about 50%, or about 20% to about 70%, or about 30% to about75%, or about 30% to about 65%, or about 35% to about 65%, or about 40%to about 60%, of an anionic surfactant.

The anionic surfactants may exist in an acid form, and the acid form maybe neutralized to form a surfactant salt. Typical agents forneutralization include metal counterion bases, such as hydroxides, e.g.,NaOH or KOH. Further suitable agents for neutralizing anionicsurfactants in their acid forms include ammonia, amines, oralkanolamines. Non-limiting examples of alkanolamines includemonoethanolamine, diethanolamine, triethanolamine, and other linear orbranched alkanolamines known in the art; suitable alkanolamines include2-amino-1-propanol, 1-aminopropanol, monoisopropanolamine, or1-amino-3-propanol. Amine neutralization may be done to a full orpartial extent, e.g., part of the anionic surfactant mix may beneutralized with sodium or potassium and part of the anionic surfactantmix may be neutralized with amines or alkanolamines.

Non-limiting examples of suitable anionic surfactants include anyconventional anionic surfactant. This may include a sulfate detersivesurfactant, for e.g., alkoxylated and/or non-alkoxylated alkyl sulfatematerials, and/or sulfonic detersive surfactants, e.g., alkyl benzenesulfonates. Suitable anionic surfactants may be derived from renewableresources, waste, petroleum, or mixtures thereof. Suitable anionicsurfactants may be linear, partially branched, branched, or mixturesthereof.

Alkoxylated alkyl sulfate materials comprise ethoxylated alkyl sulfatesurfactants, also known as alkyl ether sulfates or alkyl polyethoxylatesulfates. Examples of ethoxylated alkyl sulfates include water-solublesalts, particularly the alkali metal, ammonium and alkylolammoniumsalts, of organic sulfuric reaction products having in their molecularstructure an alkyl group containing from about 8 to about 30 carbonatoms and a sulfonic acid and its salts. (Included in the term “alkyl”is the alkyl portion of acyl groups. In some examples, the alkyl groupcontains from about 15 carbon atoms to about 30 carbon atoms. In otherexamples, the alkyl ether sulfate surfactant may be a mixture of alkylether sulfates, said mixture having an average (arithmetic mean) carbonchain length within the range of about 12 to 30 carbon atoms, and insome examples an average carbon chain length of about 12 to 15 carbonatoms, and an average (arithmetic mean) degree of ethoxylation of fromabout 1 mol to 4 mols of ethylene oxide, and in some examples an average(arithmetic mean) degree of ethoxylation of 1.8 mols of ethylene oxide.In further examples, the alkyl ether sulfate surfactant may have acarbon chain length between about 10 carbon atoms to about 18 carbonatoms, and a degree of ethoxylation of from about 1 to about 6 mols ofethylene oxide. In yet further examples, the alkyl ether sulfatesurfactant may contain a peaked ethoxylate distribution.

Non-alkoxylated alkyl sulfates may also be added to the discloseddetergent compositions and used as an anionic surfactant component.Examples of non-alkoxylated, e.g., non-ethoxylated, alkyl sulfatesurfactants include those produced by the sulfation of higher C₈-C₂₀fatty alcohols. In some examples, primary alkyl sulfate surfactants havethe general formula: ROSO₃ ⁻M⁺, wherein R is typically a linear C₈-C₂₀hydrocarbyl group, which may be straight chain or branched chain, and Mis a water-solubilizing cation. In some examples, R is a C₁₀-C₁₈ alkyl,and M is an alkali metal. In other examples, R is a C₁₂/C₁₄ alkyl and Mis sodium, such as those derived from natural alcohols.

Other useful anionic surfactants can include the alkali metal salts ofalkyl benzene sulfonates, in which the alkyl group contains from about 9to about 15 carbon atoms, in straight chain (linear) or branched chainconfiguration. In some examples, the alkyl group is linear. Such linearalkylbenzene sulfonates are known as “LAS.” In other examples, thelinear alkylbenzene sulfonate may have an average number of carbon atomsin the alkyl group of from about 11 to 14. In a specific example, thelinear straight chain alkyl benzene sulfonates may have an averagenumber of carbon atoms in the alkyl group of about 11.8 carbon atoms,which may be abbreviated as C11.8 LAS.

Suitable alkyl benzene sulphonate (LAS) may be obtained, by sulphonatingcommercially available linear alkyl benzene (LAB); suitable LAB includeslow 2-phenyl LAB, such as those supplied by Sasol under the tradenameIsochem® or those supplied by Petresa under the tradename Petrelab®,other suitable LAB include high 2-phenyl LAB, such as those supplied bySasol under the tradename Hyblene®. A suitable anionic detersivesurfactant is alkyl benzene sulphonate that is obtained by DETALcatalyzed process, although other synthesis routes, such as HF, may alsobe suitable. In one aspect a magnesium salt of LAS is used.

Another example of a suitable alkyl benzene sulfonate is a modified LAS(MLAS), which is a positional isomer that contains a branch, e.g., amethyl branch, where the aromatic ring is attached to the 2 or 3position of the alkyl chain.

The anionic surfactant may include a 2-alkyl branched primary alkylsulfates have 100% branching at the C2 position (C1 is the carbon atomcovalently attached to the alkoxylated sulfate moiety). 2-alkyl branchedalkyl sulfates and 2-alkyl branched alkyl alkoxy sulfates are generallyderived from 2-alkyl branched alcohols (as hydrophobes). 2-alkylbranched alcohols, e.g., 2-alkyl-1-alkanols or 2-alkyl primary alcohols,which are derived from the oxo process, are commercially available fromSasol, e.g., LIAL®, ISALCHEM® (which is prepared from LIAL® alcohols bya fractionation process). C14/C15 branched primary alkyl sulfate arealso commercially available, e.g., namely LIAL® 145 sulfate.

The anionic surfactant may include a mid-chain branched anionicsurfactant, e.g., a mid-chain branched anionic detersive surfactant,such as, a mid-chain branched alkyl sulphate and/or a mid-chain branchedalkyl benzene sulphonate.

Additional suitable anionic surfactants include methyl ester sulfonates,paraffin sulfonates, α-olefin sulfonates, and internal olefinsulfonates.

The compositions disclosed herein may comprise an anionic surfactantselected from the group consisting of linear or branched alkyl benzenesulfonates, linear or branched alkoxylated alkyl sulfates, linear orbranched alkyl sulfates, methyl ester sulfonates, paraffin sulfonates,α-olefin sulfonates, internal olefin sulfonates, and mixtures thereof.The compositions disclosed herein may comprise an anionic surfactantselected from the group consisting of linear or branched alkyl benzenesulfonates, linear or branched alkoxylated alkyl sulfates, linear orbranched alkyl sulfates, and mixtures thereof. The compositionsdisclosed herein may comprise a 2-alkyl branched primary alkyl sulfate.

Nonionic Surfactant

The compositions disclosed herein may comprise a nonionic surfactant.Suitable nonionic surfactants include alkoxylated fatty alcohols. Thenonionic surfactant may be selected from ethoxylated alcohols andethoxylated alkyl phenols of the formula R(OC₂H₄)_(n)OH, wherein R isselected from the group consisting of aliphatic hydrocarbon radicalscontaining from about 8 to about 15 carbon atoms and alkyl phenylradicals in which the alkyl groups contain from about 8 to about 12carbon atoms, and the average value of n is from about 5 to about 15.

Other non-limiting examples of nonionic surfactants useful hereininclude: C₈-C₁₈ alkyl ethoxylates, such as, NEODOL® nonionic surfactantsfrom Shell; C₆-C₁₂ alkyl phenol alkoxylates where the alkoxylate unitsmay be ethyleneoxy units, propyleneoxy units, or a mixture thereof;C₁₂-C₁₈ alcohol and C₆-C₁₂ alkyl phenol condensates with ethyleneoxide/propylene oxide block polymers such as Pluronic® from BASF;C₁₄-C₂₂ mid-chain branched alcohols, BA; C₁₄-C₂₂ mid-chain branchedalkyl alkoxylates, BAE_(x), wherein x is from 1 to 30;alkylpolysaccharides; specifically alkylpolyglycosides; polyhydroxyfatty acid amides; and ether capped poly(oxyalkylated) alcoholsurfactants.

Suitable nonionic detersive surfactants also include alkyl polyglucosideand alkyl alkoxylated alcohol. Suitable nonionic surfactants alsoinclude those sold under the tradename Lutensol® from BASF.

Cationic Surfactant

The compositions disclosed herein may comprise a cationic surfactant.Non-limiting examples of cationic surfactants include: the quaternaryammonium surfactants, which can have up to 26 carbon atoms include:alkoxylate quaternary ammonium (AQA) surfactants; dimethyl hydroxyethylquaternary ammonium; dimethyl hydroxyethyl lauryl ammonium chloride;polyamine cationic surfactants; cationic ester surfactants; and aminosurfactants, e.g., amido propyldimethyl amine (APA).

Suitable cationic detersive surfactants also include alkyl pyridiniumcompounds, alkyl quaternary ammonium compounds, alkyl quaternaryphosphonium compounds, alkyl ternary sulphonium compounds, and mixturesthereof.

Suitable cationic detersive surfactants are quaternary ammoniumcompounds having the general formula:(R)(R₁)(R₂)(R₃)N⁺X⁻

wherein, R is a linear or branched, substituted or unsubstituted C₆₋₁₈alkyl or alkenyl moiety, R₁ and R₂ are independently selected frommethyl or ethyl moieties, R₃ is a hydroxyl, hydroxymethyl or ahydroxyethyl moiety, X is an anion which provides charge neutrality,suitable anions include: halides, for example chloride; sulphate; andsulphonate. Suitable cationic detersive surfactants are mono-C₆₋₁₈ alkylmono-hydroxyethyl di-methyl quaternary ammonium chlorides.

Highly suitable cationic detersive surfactants are mono-C₈₋₁₀ alkylmono-hydroxyethyl di-methyl quaternary ammonium chloride, mono-C₁₀₋₁₂alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride andmono-C₁₀ alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride.

Zwitterionic Surfactant

The compositions disclosed herein may comprise a zwitterionicsurfactant. Examples of zwitterionic surfactants include: derivatives ofsecondary and tertiary amines, derivatives of heterocyclic secondary andtertiary amines, or derivatives of quaternary ammonium, quaternaryphosphonium or tertiary sulfonium compounds. Suitable examples ofzwitterionic surfactants include betaines, including alkyl dimethylbetaine and cocodimethyl amidopropyl betaine, C₈ to C₁₈ (for examplefrom C₁₂ to C₁₈) amine oxides, and sulfo and hydroxy betaines, such asN-alkyl-N,N-dimethylamino-1-propane sulfonate where the alkyl group canbe C₈ to C₁₈.

Amphoteric Surfactant

The compositions disclosed herein may comprise an amphoteric surfactant.Examples of amphoteric surfactants include aliphatic derivatives ofsecondary or tertiary amines, or aliphatic derivatives of heterocyclicsecondary and tertiary amines in which the aliphatic radical may bestraight or branched-chain and where one of the aliphatic substituentscontains at least about 8 carbon atoms, or from about 8 to about 18carbon atoms, and at least one of the aliphatic substituents contains ananionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate.Suitable amphoteric surfactants also include sarcosinates, glycinates,taurinates, and mixtures thereof.

Adjuncts

The compositions disclosed herein, particularly the dilute and compactedfluid detergents that are suitable for sale to consumers (finalproducts), may comprise adjunct ingredients. The compositions disclosedherein may comprise an adjunct selected from the group consisting of astructurant, a builder, an organic polymeric compound, an enzyme, anenzyme stabilizer, a bleach system, a brightener, a hueing agent, achelating agent, a suds suppressor, a conditioning agent, a humectant, aperfume, a perfume microcapsule, a filler or carrier, an alkalinitysystem, a pH control system, a buffer, an alkanolamine, and mixturesthereof.

Enzymes

The compositions described herein may comprise one or more enzymes whichprovide cleaning performance and/or fabric care benefits. Examples ofsuitable enzymes include, but are not limited to, hemicellulases,peroxidases, proteases, cellulases, xylanases, lipases, phospholipases,esterases, cutinases, pectinases, mannanases, pectate lyases,keratinases, reductases, oxidases, phenoloxidases, lipoxygenases,ligninases, pullulanases, tannases, pentosanases, malanases,3-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase,and amylases, or mixtures thereof. A typical combination is an enzymecocktail that may comprise, for example, a protease and lipase inconjunction with amylase. When present in a detergent composition, theaforementioned additional enzymes may be present at levels from about0.00001% to about 2%, from about 0.0001% to about 1% or even from about0.001% to about 0.5% enzyme protein by weight of the composition. Thecompositions disclosed herein may comprise from about 0.001% to about 1%by weight of an enzyme (as an adjunct), which may be selected from thegroup consisting of lipase, amylase, protease, mannanase, cellulase,pectinase, and mixtures thereof.

Enzyme Stabilizing System

The compositions may optionally comprise from about 0.001% to about 10%,or from about 0.005% to about 8%, or from about 0.01% to about 6%, byweight of the composition, of an enzyme stabilizing system. The enzymestabilizing system can be any stabilizing system which is compatiblewith the detersive enzyme. Such a system may be inherently provided byother formulation actives, or be added separately, e.g., by theformulator or by a manufacturer of detergent-ready enzymes. Suchstabilizing systems can, for example, comprise calcium ion, boric acid,propylene glycol, short chain carboxylic acids, boronic acids, chlorinebleach scavengers and mixtures thereof, and are designed to addressdifferent stabilization problems depending on the type and physical formof the detergent composition. In the case of aqueous detergentcompositions comprising protease, a reversible protease inhibitor, suchas a boron compound, including borate, 4-formyl phenylboronic acid,phenylboronic acid and derivatives thereof, or compounds such as calciumformate, sodium formate and 1,2-propane diol may be added to furtherimprove stability.

Builders

The compositions may comprise a builder. Built compositions typicallycomprise at least about 1% builder, based on the total weight of thecomposition. Liquid detergent compositions may comprise up to about 10%builder, and in some examples up to about 8% builder, of the totalweight of the composition.

Suitable builders include aluminosilicates (e.g., zeolite builders, suchas zeolite A, zeolite P, and zeolite MAP), silicates, phosphates, suchas polyphosphates (e.g., sodium tri-polyphosphate), especially sodiumsalts thereof; carbonates, bicarbonates, sesquicarbonates, and carbonateminerals other than sodium carbonate or sesquicarbonate; organic mono-,di-, tri-, and tetracarboxylates, especially water-soluble nonsurfactantcarboxylates in acid, sodium, potassium or alkanolammonium salt form, aswell as oligomeric or water-soluble low molecular weight polymercarboxylates including aliphatic and aromatic types; and phytic acid.Additional suitable builders may be selected from citric acid, lacticacid, fatty acid, polycarboxylate builders, for example, copolymers ofacrylic acid, copolymers of acrylic acid and maleic acid, and copolymersof acrylic acid and/or maleic acid, and other suitable ethylenicmonomers with various types of additional functionalities.Alternatively, the composition may be substantially free of builder.

Structurant/Thickeners

Suitable structurants/thickeners include di-benzylidene polyol acetalderivative. The fluid detergent composition may comprise from about0.01% to about 1% by weight of a dibenzylidene polyol acetal derivative(DBPA), or from about 0.05% to about 0.8%, or from about 0.1% to about0.6%, or even from about 0.3% to about 0.5%. The DBPA derivative maycomprise a dibenzylidene sorbitol acetal derivative (DBS).

Suitable structurants/thickeners also include bacterial cellulose. Thefluid detergent composition may comprise from about 0.005% to about 1%by weight of a bacterial cellulose network. The term “bacterialcellulose” encompasses any type of cellulose produced via fermentationof a bacteria of the genus Acetobacter such as CELLULON® by CPKelco U.S.and includes materials referred to popularly as microfibrillatedcellulose, reticulated bacterial cellulose, and the like.

Suitable structurants/thickeners also include coated bacterialcellulose. The bacterial cellulose may be at least partially coated witha polymeric thickener. The at least partially coated bacterial cellulosemay comprise from about 0.1% to about 5%, or even from about 0.5% toabout 3%, by weight of bacterial cellulose; and from about 10% to about90% by weight of the polymeric thickener. Suitable bacterial cellulosemay include the bacterial cellulose described above and suitablepolymeric thickeners include: carboxymethylcellulose, cationichydroxymethylcellulose, and mixtures thereof.

Suitable structurants/thickeners also include cellulose fibers. Thecomposition may comprise from about 0.01 to about 5% by weight of thecomposition of a cellulosic fiber. The cellulosic fiber may be extractedfrom vegetables, fruits or wood. Commercially available examples areAvicel® from FMC, Citri-Fi from Fiberstar or Betafib from Cosun.

Suitable structurants/thickeners also include non-polymeric crystallinehydroxyl-functional materials. The composition may comprise from about0.01 to about 1% by weight of the composition of a non-polymericcrystalline, hydroxyl functional structurant. The non-polymericcrystalline, hydroxyl functional structurants generally may comprise acrystallizable glyceride which can be pre-emulsified to aid dispersioninto the final fluid detergent composition. The crystallizableglycerides may include hydrogenated castor oil or “HCO” or derivativesthereof, provided that it is capable of crystallizing in the liquiddetergent composition.

Suitable structurants/thickeners also include polymeric structuringagents. The compositions may comprise from about 0.01% to about 5% byweight of a naturally derived and/or synthetic polymeric structurant.Examples of naturally derived polymeric structurants of use in thepresent invention include: hydroxyethyl cellulose, hydrophobicallymodified hydroxyethyl cellulose, carboxymethyl cellulose, polysaccharidederivatives and mixtures thereof. Suitable polysaccharide derivativesinclude: pectine, alginate, arabinogalactan (gum Arabic), carrageenan,gellan gum, xanthan gum, guar gum and mixtures thereof. Examples ofsynthetic polymeric structurants of use in the present inventioninclude: polycarboxylates, polyacrylates, hydrophobically modifiedethoxylated urethanes, hydrophobically modified non-ionic polyols andmixtures thereof.

Suitable structurants/thickeners also include di-amido-gellants. Theexternal structuring system may comprise a di-amido gellant having amolecular weight from about 150 g/mol to about 1,500 g/mol, or even fromabout 500 g/mol to about 900 g/mol. Such di-amido gellants may compriseat least two nitrogen atoms, wherein at least two of said nitrogen atomsform amido functional substitution groups. The amido groups may bedifferent or the same. Non-limiting examples of di-amido gellants are:N,N′-(2S,2′S)-1,1′-(dodecane-1,12-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamide;dibenzyl(2S,2'S)-1,1′-(propane-1,3-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)dicarbamate;dibenzyl(2S,2'S)-1,1′-(dodecane-1,12-diylbis(azanediyl))bis(1-oxo-3-phenylpropane-2,1-diyl)dicarbamate.

Polymeric Dispersing Agents

The cleaning composition may comprise one or more polymeric dispersingagents. Examples are carboxymethylcellulose, poly(vinyl-pyrrolidone),poly (ethylene glycol), poly(vinyl alcohol),poly(vinylpyridine-N-oxide), poly(vinylimidazole), polycarboxylates suchas polyacrylates, maleic/acrylic acid copolymers and laurylmethacrylate/acrylic acid co-polymers.

The cleaning composition may comprise one or more amphiphilic cleaningpolymers such as the compound having the following general structure:bis((C₂H₅O)(C₂H₄O)n)(CH₃)—N⁺—C_(x)H_(2x)—N⁺—(CH₃)-bis((C₂H₅O)(C₂H₄O)n),wherein n=from 20 to 30, and x=from 3 to 8, or sulphated or sulphonatedvariants thereof.

The cleaning composition may comprise amphiphilic alkoxylated greasecleaning polymers which have balanced hydrophilic and hydrophobicproperties such that they remove grease particles from fabrics andsurfaces. The amphiphilic alkoxylated grease cleaning polymers maycomprise a core structure and a plurality of alkoxylate groups attachedto that core structure. These may comprise alkoxylatedpolyalkylenimines, for example, having an inner polyethylene oxide blockand an outer polypropylene oxide block. Such compounds may include, butare not limited to, ethoxylated polyethyleneimine, ethoxylatedhexamethylene diamine, and sulfated versions thereof. Polypropoxylatedderivatives may also be included. A wide variety of amines andpolyalklyeneimines can be alkoxylated to various degrees. A usefulexample is 600 g/mol polyethyleneimine core ethoxylated to 20 EO groupsper NH and is available from BASF. The detergent compositions describedherein may comprise from about 0.1% to about 10%, and in some examples,from about 0.1% to about 8%, and in other examples, from about 0.1% toabout 6%, by weight of the detergent composition, of alkoxylatedpolyamines.

Carboxylate polymer—The detergent composition may also include one ormore carboxylate polymers, which may optionally be sulfonated. Suitablecarboxylate polymers include a maleate/acrylate random copolymer or apoly(meth)acrylate homopolymer. In one aspect, the carboxylate polymeris a poly(meth)acrylate homopolymer having a molecular weight from 4,000Da to 9,000 Da, or from 6,000 Da to 9,000 Da.

Alkoxylated polycarboxylates may also be used in the detergentcompositions herein to provide grease removal. Such materials aredescribed in WO 91/08281 and PCT 90/01815. Chemically, these materialscomprise poly(meth)acrylates having one ethoxy side-chain per every 7-8(meth)acrylate units. The side-chains are of the formula —(CH₂CH₂O)_(m)(CH₂)_(n)CH₃ wherein m is 2-3 and n is 6-12. The side-chains areester-linked to the polyacrylate “backbone” to provide a “comb” polymertype structure. The molecular weight can vary, but may be in the rangeof about 2000 to about 50,000. The detergent compositions describedherein may comprise from about 0.1% to about 10%, and in some examples,from about 0.25% to about 5%, and in other examples, from about 0.3% toabout 2%, by weight of the detergent composition, of alkoxylatedpolycarboxylates.

The compositions may include an amphiphilic graft co-polymer. A suitableamphiphilic graft co-polymer comprises (i) a polyethyelene glycolbackbone; and (ii) and at least one pendant moiety selected frompolyvinyl acetate, polyvinyl alcohol and mixtures thereof. A suitableamphilic graft co-polymer is Sokalan® HP22, supplied from BASF. Suitablepolymers include random graft copolymers, preferably a polyvinyl acetategrafted polyethylene oxide copolymer having a polyethylene oxidebackbone and multiple polyvinyl acetate side chains. The molecularweight of the polyethylene oxide backbone is typically about 6000 andthe weight ratio of the polyethylene oxide to polyvinyl acetate is about40 to 60 and no more than 1 grafting point per 50 ethylene oxide units.

Soil Release Polymer

The detergent compositions of the present invention may also include oneor more soil release polymers having a structure as defined by one ofthe following structures (I), (II) or (III):—[(OCHR¹—CHR²)_(a)—O—OC—Ar—CO—]_(d)  (I)—[(OCHR³—CHR⁴)_(b)—O—OC-sAr—CO—]_(e)  (II)—[(OCHR⁵—CHR⁶)_(c)—OR⁷]_(f)  (III)

wherein:

a, b and c are from 1 to 200;

d, e and f are from 1 to 50;

Ar is a 1,4-substituted phenylene;

-   -   sAr is 1,3-substituted phenylene substituted in position 5 with        SO₃Me;

Me is Li, K, Mg/2, Ca/2, Al/3, ammonium, mono-, di-, tri-, ortetraalkylammonium wherein the alkyl groups are C₁-C₁₈ alkyl or C₂-C₁₀hydroxyalkyl, or mixtures thereof;

R¹, R², R³, R⁴, R⁵ and R⁶ are independently selected from H or C₁-C₁₈ n-or iso-alkyl; and R⁷ is a linear or branched C1-Cis alkyl, or a linearor branched C₂-C₃₀ alkenyl, or a cycloalkyl group with 5 to 9 carbonatoms, or a C₈-C₃₀ aryl group, or a C₆-C₃₀ arylalkyl group.

Suitable soil release polymers are polyester soil release polymers suchas Repel-o-tex polymers, including Repel-o-tex SF, SF-2 and SRP6supplied by Rhodia. Other suitable soil release polymers include Texcarepolymers, including Texcare SRA100, SRA300, SRN100, SRN170, SRN240,SRN300 and SRN325 supplied by Clariant. Other suitable soil releasepolymers are Marloquest polymers, such as Marloquest SL supplied bySasol.

Cellulosic Polymer

The cleaning compositions of the present invention may also include oneor more cellulosic polymers including those selected from alkylcellulose, alkyl alkoxyalkyl cellulose, carboxyalkyl cellulose, alkylcarboxyalkyl cellulose. In one aspect, the cellulosic polymers areselected from the group comprising carboxymethyl cellulose, methylcellulose, methyl hydroxyethyl cellulose, methyl carboxymethylcellulose, and mixtures thereof. In one aspect, the carboxymethylcellulose has a degree of carboxymethyl substitution from 0.5 to 0.9 anda molecular weight from 100,000 Da to 300,000 Da.

Amines

Additional amines may be used in the compositions described herein foradded removal of grease and particulates from soiled materials. Thecompositions described herein may comprise from about 0.1% to about 10%,or from about 0.1% to about 4%, or from about 0.1% to about 2%, byweight of the composition, of additional amines. Non-limiting examplesof additional amines include, but are not limited to, polyetheramines,polyamines, oligoamines, triamines, diamines, pentamines, tetraamines,or combinations thereof. Specific examples of suitable additional aminesinclude tetraethylenepentamine, triethylenetetraamine,diethylenetriamine, or a mixture thereof.

Bleaching Agents

The detergent compositions of the present invention may comprise one ormore bleaching agents. Suitable bleaching agents other than bleachingcatalysts include photobleaches, bleach activators, hydrogen peroxide,sources of hydrogen peroxide, pre-formed peracids and mixtures thereof.In general, when a bleaching agent is used, the detergent compositionsof the present invention may comprise from about 0.1% to about 50% oreven from about 0.1% to about 25% bleaching agent by weight of thedetergent composition.

Bleach Catalysts

The detergent compositions of the present invention may also include oneor more bleach catalysts capable of accepting an oxygen atom from aperoxyacid and/or salt thereof, and transferring the oxygen atom to anoxidizeable substrate. Suitable bleach catalysts include, but are notlimited to: iminium cations and polyions; iminium zwitterions; modifiedamines; modified amine oxides; N-sulphonyl imines; N-phosphonyl imines;N-acyl imines; thiadiazole dioxides; perfluoroimines; cyclic sugarketones and mixtures thereof.

Brighteners

Optical brighteners or other brightening or whitening agents may beincorporated at levels of from about 0.01% to about 1.2%, by weight ofthe composition, into the detergent compositions described herein.Commercial fluorescent brighteners suitable for the present inventioncan be classified into subgroups, including but not limited to:derivatives of stilbene, pyrazoline, coumarin, benzoxazoles, carboxylicacid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and6-membered-ring heterocycles, and other miscellaneous agents.

In some examples, the fluorescent brightener is selected from the groupconsisting of disodium4,4′-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2′-stilbenedisulfonate(brightener 15, commercially available under the tradename TinopalAMS-GX by Ciba Geigy Corporation), disodium4,4′-bis{[4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl]-amino}-2,2′-stilbenedisulonate(commercially available under the tradename Tinopal UNPA-GX byCiba-Geigy Corporation), disodium4,4′-bis{[4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl]-amino}-2,2′-stilbenedisulfonate(commercially available under the tradename Tinopal 5BM-GX by Ciba-GeigyCorporation). More preferably, the fluorescent brightener is disodium4,4′-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2′-stilbenedisulfonate.

The brighteners may be added in particulate form or as a premix with asuitable solvent, for example nonionic surfactant, propanediol.

Fabric Hueing Agents

The composition may comprise a fabric hueing agent (sometimes referredto as shading, bluing or whitening agents). Typically the hueing agentprovides a blue or violet shade to fabric. Hueing agents can be usedeither alone or in combination to create a specific shade of hueingand/or to shade different fabric types. This may be provided for exampleby mixing a red and green-blue dye to yield a blue or violet shade.Hueing agents may be selected from any known chemical class of dye,including but not limited to acridine, anthraquinone (includingpolycyclic quinones), azine, azo (e.g., monoazo, disazo, trisazo,tetrakisazo, polyazo), including premetallized azo, benzodifurane andbenzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine,diphenylmethane, formazan, hemicyanine, indigoids, methane,naphthalimides, naphthoquinone, nitro and nitroso, oxazine,phthalocyanine, pyrazoles, stilbene, styryl, triarylmethane,triphenylmethane, xanthenes and mixtures thereof.

Suitable fabric hueing agents include dyes, dye-clay conjugates, andorganic and inorganic pigments. Suitable dyes also include smallmolecule dyes and polymeric dyes. Suitable small molecule dyes includesmall molecule dyes selected from the group consisting of dyes fallinginto the Colour Index (C.I.) classifications of Direct, Basic, Reactiveor hydrolysed Reactive, Solvent or Disperse dyes for example that areclassified as Blue, Violet, Red, Green or Black, and provide the desiredshade either alone or in combination. Suitable polymeric dyes includepolymeric dyes selected from the group consisting of polymers containingcovalently bound (sometimes referred to as conjugated) chromogens,(dye-polymer conjugates), for example polymers with chromogensco-polymerized into the backbone of the polymer and mixtures thereof.Suitable polymeric dyes also include polymeric dyes selected from thegroup consisting of fabric-substantive colorants sold under the name ofLiquitint® (Milliken, Spartanburg, S.C., USA), dye-polymer conjugatesformed from at least one reactive dye and a polymer selected from thegroup consisting of polymers comprising a moiety selected from the groupconsisting of a hydroxyl moiety, a primary amine moiety, a secondaryamine moiety, a thiol moiety and mixtures thereof. Suitable polymericdyes also include polymeric dyes selected from the group consisting ofLiquitint® Violet CT, carboxymethyl cellulose (CMC) covalently bound toa reactive blue, reactive violet or reactive red dye such as CMCconjugated with C.I. Reactive Blue 19, sold by Megazyme, Wicklow,Ireland under the product name AZO-CM-CELLULOSE, product code S-ACMC,alkoxylated triphenyl-methane polymeric colourants, alkoxylatedthiophene polymeric colourants, and mixtures thereof.

The aforementioned fabric hueing agents can be used in combination (anymixture of fabric hueing agents can be used).

Encapsulates

The compositions may comprise an encapsulate. The encapsulate maycomprise a core, a shell having an inner and outer surface, where theshell encapsulates the core.

The encapsulate may comprise a core and a shell, where the corecomprises a material selected from perfumes; brighteners; dyes; insectrepellants; silicones; waxes; flavors; vitamins; fabric softeningagents; skin care agents, e.g., paraffins; enzymes; anti-bacterialagents; bleaches; sensates; or mixtures thereof; and where the shellcomprises a material selected from polyethylenes; polyamides;polyvinylalcohols, optionally containing other co-monomers;polystyrenes; polyisoprenes; polycarbonates; polyesters; polyacrylates;polyolefins; polysaccharides, e.g., alginate and/or chitosan; gelatin;shellac; epoxy resins; vinyl polymers; water insoluble inorganics;silicone; aminoplasts, or mixtures thereof. When the shell comprises anaminoplast, the aminoplast may comprise polyurea, polyurethane, and/orpolyureaurethane. The polyurea may comprise polyoxymethyleneurea and/ormelamine formaldehyde.

The encapsulate may comprise a core, and the core may comprise aperfume. The encapsulate may comprise a shell, and the shell maycomprise melamine formaldehyde and/or cross linked melamineformaldehyde. The encapsulate may comprise a core comprising a perfumeand a shell comprising melamine formaldehyde and/or cross linkedmelamine formaldehyde

Suitable encapsulates may comprise a core material and a shell, wherethe shell at least partially surrounds the core material. The core ofthe encapsulate comprises a material selected from a perfume rawmaterial and/or optionally another material, e.g., vegetable oil, estersof vegetable oils, esters, straight or branched chain hydrocarbons,partially hydrogenated terphenyls, dialkyl phthalates, alkyl biphenyls,alkylated naphthalene, petroleum spirits, aromatic solvents, siliconeoils, or mixtures thereof.

The wall of the encapsulate may comprise a suitable resin, such as thereaction product of an aldehyde and an amine. Suitable aldehydes includeformaldehyde. Suitable amines include melamine, urea, benzoguanamine,glycoluril, or mixtures thereof. Suitable melamines include methylolmelamine, methylated methylol melamine, imino melamine and mixturesthereof. Suitable ureas include, dimethylol urea, methylated dimethylolurea, urea-resorcinol, or mixtures thereof.

Suitable formaldehyde scavengers may be employed with the encapsulates,for example, in a capsule slurry and/or added to a composition before,during, or after the encapsulates are added to such composition.

Suitable capsules can be purchased from Appleton Papers Inc. ofAppleton, Wis. USA.

Perfumes

Perfumes and perfumery ingredients may be used in the detergentcompositions described herein. Non-limiting examples of perfume andperfumery ingredients include, but are not limited to, aldehydes,ketones, esters, and the like. Other examples include various naturalextracts and essences which can comprise complex mixtures ofingredients, such as orange oil, lemon oil, rose extract, lavender,musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar, andthe like. Finished perfumes can comprise extremely complex mixtures ofsuch ingredients. Finished perfumes may be included at a concentrationranging from about 0.01% to about 2% by weight of the detergentcomposition.

Dye Transfer Inhibiting Agents

Fabric detergent compositions may also include one or more materialseffective for inhibiting the transfer of dyes from one fabric to anotherduring the cleaning process. Generally, such dye transfer inhibitingagents may include polyvinyl pyrrolidone polymers, polyamine N-oxidepolymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,manganese phthalocyanine, peroxidases, and mixtures thereof. If used,these agents may be used at a concentration of about 0.0001% to about10%, by weight of the composition, in some examples, from about 0.01% toabout 5%, by weight of the composition, and in other examples, fromabout 0.05% to about 2% by weight of the composition.

Chelating Agents

The detergent compositions described herein may also contain one or moremetal ion chelating agents. Suitable molecules include copper, ironand/or manganese chelating agents and mixtures thereof. Such chelatingagents can be selected from the group consisting of phosphonates, aminocarboxylates, amino phosphonates, succinates,polyfunctionally-substituted aromatic chelating agents,2-pyridinol-N-oxide compounds, hydroxamic acids, carboxymethyl inulinsand mixtures thereof. Chelating agents can be present in the acid orsalt form including alkali metal, ammonium, and substituted ammoniumsalts thereof, and mixtures thereof. Other suitable chelating agents foruse herein are the commercial DEQUEST series, and chelants fromMonsanto, Akzo-Nobel, DuPont, Dow, the Trilon® series from BASF andNalco.

The chelant may be present in the detergent compositions disclosedherein at from about 0.005% to about 15% by weight, about 0.01% to about5% by weight, about 0.1% to about 3.0% by weight, or from about 0.2% toabout 0.7% by weight, or from about 0.3% to about 0.6% by weight of thedetergent compositions disclosed herein.

Suds Suppressors

Compounds for reducing or suppressing the formation of suds can beincorporated into the detergent compositions described herein. Sudssuppression can be of particular importance in the so-called “highconcentration cleaning process” and in front-loading style washingmachines. The detergent compositions herein may comprise from 0.1% toabout 10%, by weight of the composition, of suds suppressor.

Examples of suds suppressors include monocarboxylic fatty acid andsoluble salts therein, high molecular weight hydrocarbons such asparaffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acidesters of monovalent alcohols, aliphatic C₁₈-C₄₀ ketones (e.g.,stearone), N-alkylated amino triazines, waxy hydrocarbons preferablyhaving a melting point below about 100° C., silicone suds suppressors,and secondary alcohols.

Additional suitable antifoams are those derived from phenylpropylmethylsubstituted polysiloxanes.

The detergent composition may comprise a suds suppressor selected fromorganomodified silicone polymers with aryl or alkylaryl substituentscombined with silicone resin and a primary filler, which is modifiedsilica. The detergent compositions may comprise from about 0.001% toabout 4.0%, by weight of the composition, of such a suds suppressor.

The detergent composition comprises a suds suppressor selected from: a)mixtures of from about 80 to about 92% ethylmethyl,methyl(2-phenylpropyl) siloxane; from about 5 to about 14% MQ resin inoctyl stearate; and from about 3 to about 7% modified silica; b)mixtures of from about 78 to about 92% ethylmethyl,methyl(2-phenylpropyl) siloxane; from about 3 to about 10% MQ resin inoctyl stearate; from about 4 to about 12% modified silica; or c)mixtures thereof, where the percentages are by weight of the anti-foam.

Suds Boosters

If high sudsing is desired, suds boosters such as the C₁₀-C₁₆alkanolamides may be incorporated into the detergent compositions at aconcentration ranging from about 1% to about 10% by weight of thedetergent composition. Some examples include the C₁₀-C₁₄ monoethanol anddiethanol amides. If desired, water-soluble magnesium and/or calciumsalts such as MgCl₂, MgSO₄, CaCl₂, CaSO₄, and the like, may be added atlevels of about 0.1% to about 2% by weight of the detergent composition,to provide additional suds and to enhance grease removal performance.

Conditioning Agents

The composition of the present invention may include a high meltingpoint fatty compound.

The high melting point fatty compound useful herein has a melting pointof 25° C. or higher, and is selected from the group consisting of fattyalcohols, fatty acids, fatty alcohol derivatives, fatty acidderivatives, and mixtures thereof. Such compounds of low melting pointare not intended to be included in this section. The high melting pointfatty compound is included in the composition at a level of from about0.1% to about 40%, preferably from about 1% to about 30%, morepreferably from about 1.5% to about 16% by weight of the composition,from about 1.5% to about 8%.

The composition of the present invention may include a nonionic polymeras a conditioning agent.

Suitable conditioning agents for use in the composition include thoseconditioning agents characterized generally as silicones (e.g., siliconeoils, cationic silicones, silicone gums, high refractive silicones, andsilicone resins), organic conditioning oils (e.g., hydrocarbon oils,polyolefins, and fatty esters) or combinations thereof, or thoseconditioning agents which otherwise form liquid, dispersed particles inthe aqueous surfactant matrix herein. The concentration of the siliconeconditioning agent typically ranges from about 0.01% to about 10%.

The compositions of the present invention may also comprise from about0.05% to about 3% of at least one organic conditioning oil as theconditioning agent, either alone or in combination with otherconditioning agents, such as the silicones (described herein). Suitableconditioning oils include hydrocarbon oils, polyolefins, and fattyesters.

Fabric Enhancement Polymers

Suitable fabric enhancement polymers are typically cationically chargedand/or have a high molecular weight. Suitable concentrations of thiscomponent are in the range from 0.01% to 50%, preferably from 0.1% to15%, more preferably from 0.2% to 5.0%, and most preferably from 0.5% to3.0% by weight of the composition. The fabric enhancement polymers maybe a homopolymer or be formed from two or more types of monomers. Themonomer weight of the polymer will generally be between 5,000 and10,000,000, typically at least 10,000 and preferably in the range100,000 to 2,000,000. Preferred fabric enhancement polymers will havecationic charge densities of at least 0.2 meq/gm, preferably at least0.25 meq/gm, more preferably at least 0.3 meq/gm, but also preferablyless than 5 meq/gm, more preferably less than 3 meq/gm, and mostpreferably less than 2 meq/gm at the pH of intended use of thecomposition, which pH will generally range from pH 3 to pH 9, preferablybetween pH 4 and pH 8. The fabric enhancement polymers may be of naturalor synthetic origin.

Pearlescent Agent

The laundry detergent compositions of the invention may comprise apearlescent agent. Non-limiting examples of pearlescent agents include:mica; titanium dioxide coated mica; bismuth oxychloride; fish scales;mono and diesters of alkylene glycol. The pearlescent agent may beethyleneglycoldistearate (EGDS).

Hygiene and Malodour

The compositions of the present invention may also comprise one or moreof zinc ricinoleate, thymol, quaternary ammonium salts such as Bardac®,polyethylenimines (such as Lupasol® from BASF) and zinc complexesthereof, silver and silver compounds, especially those designed toslowly release Ag⁺ or nano-silver dispersions.

Buffer System

The detergent compositions described herein may be formulated such that,during use in aqueous cleaning operations, the wash water will have a pHof between about 7.0 and about 12, and in some examples, between about7.0 and about 11. Techniques for controlling pH at recommended usagelevels include the use of buffers, alkalis, or acids, and are well knownto those skilled in the art. These include, but are not limited to, theuse of sodium carbonate, citric acid or sodium citrate, lactic acid orlactate, monoethanol amine or other amines, boric acid or borates, andother pH-adjusting compounds well known in the art.

The detergent compositions herein may comprise dynamic in-wash pHprofiles. Such detergent compositions may use wax-covered citric acidparticles in conjunction with other pH control agents such that (i)about 3 minutes after contact with water, the pH of the wash liquor isgreater than 10; (ii) about 10 minutes after contact with water, the pHof the wash liquor is less than 9.5; (iii) about 20 minutes aftercontact with water, the pH of the wash liquor is less than 9.0; and (iv)optionally, wherein, the equilibrium pH of the wash liquor is in therange of from about 7.0 to about 8.5.

Water-Soluble Film

The compositions of the present disclosure may be encapsulated within awater-soluble film, for example, a film comprising polyvinyl alcohol(PVOH).

Other Adjunct Ingredients

A wide variety of other ingredients may be used in the detergentcompositions herein, including other active ingredients, carriers,hydrotropes, processing aids, dyes or pigments, solvents for liquidformulations, and solid or other liquid fillers, erythrosine, colliodalsilica, waxes, probiotics, surfactin, aminocellulosic polymers, ZincRicinoleate, perfume microcapsules, rhamnolipids, sophorolipids,glycopeptides, methyl ester sulfonates, methyl ester ethoxylates,sulfonated estolides, cleavable surfactants, biopolymers, silicones,modified silicones, aminosilicones, deposition aids, locust bean gum,cationic hydroxyethylcellulose polymers, cationic guars, hydrotropes(especially cumenesulfonate salts, toluenesulfonate salts,xylenesulfonate salts, and naphalene salts), antioxidants, BHT, PVAparticle-encapsulated dyes or perfumes, pearlescent agents, effervescentagents, color change systems, silicone polyurethanes, opacifiers, tabletdisintegrants, biomass fillers, fast-dry silicones, glycol distearate,hydroxyethylcellulose polymers, hydrophobically modified cellulosepolymers or hydroxyethylcellulose polymers, starch perfume encapsulates,emulsified oils, bisphenol antioxidants, microfibrous cellulosestructurants, properfumes, styrene/acrylate polymers, triazines, soaps,superoxide dismutase, benzophenone protease inhibitors, functionalizedTiO2, dibutyl phosphate, silica perfume capsules, and other adjunctingredients, silicate salts (e.g., sodium silicate, potassium silicate),choline oxidase, pectate lyase, mica, titanium dioxide coated mica,bismuth oxychloride, and other actives.

The compositions described herein may also contain vitamins and aminoacids such as: water soluble vitamins and their derivatives, watersoluble amino acids and their salts and/or derivatives, water insolubleamino acids viscosity modifiers, dyes, nonvolatile solvents or diluents(water soluble and insoluble), pearlescent aids, foam boosters,additional surfactants or nonionic cosurfactants, pediculocides, pHadjusting agents, perfumes, preservatives, chelants, proteins, skinactive agents, sunscreens, UV absorbers, vitamins, niacinamide,caffeine, and minoxidil.

The compositions of the present invention may also contain pigmentmaterials such as nitroso, monoazo, disazo, carotenoid, triphenylmethane, triaryl methane, xanthene, quinoline, oxazine, azine,anthraquinone, indigoid, thionindigoid, quinacridone, phthalocianine,botanical, and natural colors, including water soluble components suchas those having C.I. Names. The detergent compositions of the presentinvention may also contain antimicrobial agents.

Water

The compositions disclosed herein may comprise from about 1% to about80%, by weight of the composition, water. When the composition is aheavy duty liquid detergent composition, the composition typicallycomprises from about 40% to about 80% water. When the composition is acompact liquid detergent, the composition typically comprises from about20% to about 60%, or from about 30% to about 50% water. When thecomposition is in unit dose form, for example, encapsulated inwater-soluble film, the composition typically comprises less than 20%,or less than 15%, or less than 12%, or less than 10%, or less than 8%,or less than 5% water. The composition may comprise from about 1% to20%, or from about 3% to about 15%, or from about 5% to about 12%, byweight of the composition, water. When the composition is in unitizeddose form, for example, encapsulated in water-soluble film, thecomposition typically comprises less than 20%, or less than 15%, or lessthan 12%, or less than 10%, or less than 8%, or less than 5% water. Thecomposition may comprise from about 1% to 20%, or from about 3% to about15%, or from about 5% to about 12%, by weight of the composition, water.

Methods of Use

The present invention includes methods for cleaning soiled material.Compact fluid detergent compositions that are suitable for sale toconsumers are suited for use in laundry pretreatment applications,laundry cleaning applications, and home care applications.

Such methods include, but are not limited to, the steps of contactingdetergent compositions in neat form or diluted in wash liquor, with atleast a portion of a soiled material and then optionally rinsing thesoiled material. The soiled material may be subjected to a washing stepprior to the optional rinsing step.

For use in laundry pretreatment applications, the method may includecontacting the detergent compositions described herein with soiledfabric. Following pretreatment, the soiled fabric may be laundered in awashing machine or otherwise rinsed.

Machine laundry methods may comprise treating soiled laundry with anaqueous wash solution in a washing machine having dissolved or dispensedtherein an effective amount of a machine laundry detergent compositionin accord with the invention. An “effective amount” of the detergentcomposition means from about 20 g to about 300 g of product dissolved ordispersed in a wash solution of volume from about 5 L to about 65 L. Thewater temperatures may range from about 5° C. to about 100° C. The waterto soiled material (e.g., fabric) ratio may be from about 1:1 to about30:1. The compositions may be employed at concentrations of from about500 ppm to about 15,000 ppm in solution. In the context of a fabriclaundry composition, usage levels may also vary depending not only onthe type and severity of the soils and stains, but also on the washwater temperature, the volume of wash water, and the type of washingmachine (e.g., top-loading, front-loading, top-loading, vertical-axisJapanese-type automatic washing machine).

The detergent compositions herein may be used for laundering of fabricsat reduced wash temperatures. These methods of laundering fabriccomprise the steps of delivering a laundry detergent composition towater to form a wash liquor and adding a laundering fabric to said washliquor, wherein the wash liquor has a temperature of from about 0° C. toabout 20° C., or from about 0° C. to about 15° C., or from about 0° C.to about 9° C. The fabric may be contacted to the water prior to, orafter, or simultaneous with, contacting the laundry detergentcomposition with water.

Another method includes contacting a nonwoven substrate, which isimpregnated with the detergent composition, with a soiled material. Asused herein, “nonwoven substrate” can comprise any conventionallyfashioned nonwoven sheet or web having suitable basis weight, caliper(thickness), absorbency, and strength characteristics. Non-limitingexamples of suitable commercially available nonwoven substrates includethose marketed under the tradenames SONTARA® by DuPont and POLYWEB® byJames River Corp.

Hand washing/soak methods, and combined handwashing with semi-automaticwashing machines, are also included.

Packaging for the Compositions

The compact fluid detergent compositions that are suitable for consumeruse can be packaged in any suitable container including thoseconstructed from paper, cardboard, plastic materials, and any suitablelaminates. The compact fluid detergent compositions may also beencapsulated in water-soluble film and packaged as a unitized dosedetergent composition, for example, mono-compartment pouches ormulti-compartment pouches having superposed and/or side-by-sidecompartments.

EXAMPLES

In the following examples, the individual ingredients within thecleaning compositions are expressed as percentages by weight of thecleaning compositions.

Synthesis Examples

¹H-NMR and ¹³C-NMR measurements are carried out in CDCl₃ with a Bruker400 MHz spectrometer.

The degree of amination is calculated from the total amine value (AZ)divided by sum of the total acetylables value (AC) and tertiary aminevalue(tert. AZ) multiplied by 100: (Total AZ: (AC+tert. AZ)×100). Thetotal amine value (AZ) is determined according to DIN 16945. The totalacetylables value (AC) is determined according to DIN 53240. Thesecondary and tertiary amine are determined according to ASTM D2074-07.The primary amines value is calculated as follows: primary aminevalue=AZ−secondary+tertiary amine value. Primary amine in % of totalamine is calculated as follows: Primary amine in%=((AZ−secondary+tertiary amine value)/AZ)*100. The hydroxyl value iscalculated from (total acetylables value+tertiary amine value)−totalamine value.

Example 1 Example 1a: 1 mol 2-butyl-2-ethyl-1,3-propandiol+2 molPropylene Oxide

In a 21 autoclave 495.7 g 2-butyl-2-ethyl-1,3-propane diol and 1.7 gpotassium tert.-butylat are mixed. The autoclave is purged three timeswith nitrogen and heated to 140° C. 359.3 g propylene oxide is addedwithin 5 hours. The mixture is allowed to post-react for 4 hours at 140°C. The reaction mixture is stripped with nitrogen and volatile compoundsare removed in vacuo at 80° C. The catalyst is removed by adding 26.2 gMacrosorb MP5plus, stirring at 100° C. for 2 hours and filtration. Ayellowish oil is obtained (873.0 g, hydroxyl value: 386.6 mgKOH/g).

Example 1b: 1 mol 2-butyl-2-ethyl-1,3-propandiol+2 mol propylene oxide+2mol Acrylonitrile

In a 4-neck vessel with stirrer, thermometer, reflux condenser, nitrogeninlet, and dropping funnel, 276.4 g of product from example 1a isplaced. 2.3 g of a 50% aqueous solution of tetrakis (2-hydroxyethyl)ammonium hydroxide is added at room temperature. The mixture is heatedto 60° C. and 109.3 g acrylonitrile is added dropwise at 60° C. Afterstirring for 1.5 hours at given temperature, the mixture is stirred foradditional 14 hours at room temperature. The reaction product isfiltered and excess acrylonitrile is removed in vacuo. An orange liquidis obtained (370.0 g, water 0.1%). Complete conversion of acrylonitrileis detected by ¹H-NMR in CDCl₃.

Example 1c: 1 mol 2-butyl-2-ethyl-1,3-propandiol+2 mol Propylene oxide+2mol Acrylonitrile, Hydrogenated

Representative Procedure for the hydrogenation of cyanoethylatedpolyoxyalkylenes: The hydrogenation of example 1b is conducted in atubular reactor (length 500 mm, diameter 18 mm) filled with a splittedcobalt catalyst prepared as described in EP636409. At a temperature of110° C. and a pressure of 160 bar, the nitrile (20 wt.-% in THF) istogether with ammonia and hydrogen continuously fed into the reactor atsuch a rate that full conversion of the nitrile is assured. The crudematerial is collected and stripped on a rotary evaporator to removeexcess ammonia, light weight amines and THF to produce the hydrogenatedmaterial. The analytical data of the reaction product is shown below.

Total amine Secondary + tertiary Tertiary amine value amine value value[mg KOH/g] [mg KOH/g] [mg KOH/g] 264.8 1.17 0.66

Example 2 Example 2a: 1 mol 2-butyl-2-ethyl-1,3-propandiol+4 molPropylene Oxide

In a 2 l autoclave, 411.0 g 2-butyl-2-ethyl-1,3-propane diol and 2.0 gpotassium tert.-butylate are mixed. The autoclave is purged three timeswith nitrogen and heated to 140° C. 596.8 g propylene oxide is addedwithin 8 hours. The mixture is allowed to post-react for 6 hours at 140°C. The reaction mixture is stripped with nitrogen and volatile compoundsare removed in vacuo at 80° C. The catalyst is removed by adding 30.2 gMacrosorb MP5plus, stirring at 100° C. for 2 hours and filtration. Ayellowish oil is obtained (1001.0 g, hydroxyl value: 273.1 mgKOH/g).

Example 2b: 1 mol 2-butyl-2-ethyl-1,3-propandiol+4 mol Propyleneoxide+1.2 mol Acrylonitrile

In a 4-neck vessel with stirrer, thermometer, reflux condenser, nitrogeninlet, and dropping funnel, 314.1 g of product from example 2a isplaced. 6.0 g of a 50% aqueous solution of tetrakis (2-hydroxyethyl)ammonium hydroxide is added at room temperature. The mixture is heatedto 60° C. and 89.0 g acrylonitrile is added dropwise at 60° C. Afterstirring for 3 hours at given temperature, the mixture is stirred foradditional 14 hours at room temperature. The reaction product isfiltered and excess acrylonitrile is removed in vacuo. An orange liquidis obtained (354.0 g). Complete conversion of acrylonitrile is detectedby ¹H-NMR in CDCl3. The degree of functionalization with acrylonitrileis detected by ¹H-NMR in CDCl3 (peak at 2.6 ppm).

Example 2c: 1 mol 2-butyl-2-ethyl-1,3-propandiol+4 mol Propyleneoxide+1.2 mol Acrylonitrile, Hydrogenated

Example 2b is hydrogenated according to the representative proceduredescribed in example 1c. The analytical data of the reaction product areshown below.

Total amine Secondary + tertiary Tertiary amine value amine value value[mg KOH/g] [mg KOH/g] [mg KOH/g] 145.2 3.83 3.19

Example 3 Comparative Example 3a: 1 mol 2-butyl-2-ethyl-1,3-propandiol+4mol Propylene Oxide

In a 2 l autoclave, 322.6 g 2-Butyl-2-ethyl-1,3-propane diol and 7.9 gKOH (50% in water) are mixed and stirred under vacuum (<10 mbar) at 120°C. for 2 h. The autoclave is purged with nitrogen and heated to 140° C.467.8 g propylene oxide is added in portions within 6 h. To complete thereaction, the mixture is allowed to post-react for additional 5 h at140° C. The reaction mixture is stripped with nitrogen and volatilecompounds are removed in vacuo at 80° C. The catalyst potassiumhydroxide is removed by adding 2.3 g synthetic magnesium silicate(Macrosorb MP5plus, Ineos Silicas Ltd.), stirring at 100° C. for 2 h andfiltration. A yellowish oil is obtained (772.0 g, hydroxyl value: 248.5mgKOH/g).

Comparative Example 3b: 1 mol 2-butyl-2-ethyl-1,3-propandiol+4 molPropylene Oxide, Aminated

In a 9 l autoclave, 600 g of the resulting diol mixture from example 3a,1250 g THF and 1500 g ammonia are mixed in presence of 200 ml of a solidcatalyst, as described in EP0696572B1. The catalyst containing nickel,cobalt, copper, molybdenum and zirconium is in the form of 3×3 mmtables. The autoclave is purged with hydrogen and the reaction isstarted by heating the autoclave. The reaction mixture is stirred for 18h at 205° C., the total pressure is maintained at 270 bar by purginghydrogen during the entire reductive amination step. After cooling downthe autoclave, the final product is collected, filtered, vented ofexcess ammonia and stripped in a rotary evaporator to remove lightamines and water. A total of 560 grams of a low-color etheramine mixtureis recovered. The analytical results thereof are shown below.

Total Total Secondary Tertiary Primary amine- acetylatables and tertiaryamine- Hydroxyl Degree of Amine value value value amine value valuevalue amination in % of total mg KOH/g mg KOH/g mg KOH/g mg KOH/g mgKOH/g in % amine 278.21 287.70 6.96 4.60 14.09 95.18 97.50

Example 4 Comparative Example 4a: 1 mol2-butyl-2-ethyl-1,3-propandiol+5.6 mol Propylene Oxide

In a 2 l autoclave, 313.1 g 2-Butyl-2-ethyl-1,3-propane diol and 3.8 gKOH (50% in water) are mixed and stirred under vacuum (<10 mbar) at 120°C. for 2 h. The autoclave is purged with nitrogen and heated to 140° C.635.6 g propylene oxide is added in portions within 6 h. To complete thereaction, the mixture is allowed to post-react for additional 5 h at140° C. The reaction mixture is stripped with nitrogen and volatilecompounds are removed in vacuo at 80° C. The catalyst is removed byadding 50.9 g water and 8.2 g phosphoric acid (40% in water) stirring at100° C. for 0.5 h and dewatering in vacuo for 2 hours. After filtration,930.0 g of a light yellowish oil is obtained (hydroxyl value: 233mgKOH/g).

Comparative Example 4b: 1 mol 2-butyl-2-ethyl-1,3-propandiol+5.6 molPropylene Oxide, Partially Aminated

The amination of the product from example 4a is conducted in a tubularreactor (length 500 mm, diameter 18 mm) which is charged with 15 mL ofsilica (3×3 mm pellets) followed by 70 mL (74 g) of the catalystprecursor (containing oxides of nickel, cobalt, copper and tin ongamma-Al₂O₃, 1.0-1.6 mm split—prepared according to WO 2013/072289 A1)and filled up with silica (ca. 15 mL).

The catalyst is activated at atmospheric pressure by being heated to100° C. with 25 norm litre (Nl)/h of nitrogen, then 3 hours at 150° C.in which the hydrogen feed was increased from 2 to Nl/h, then heated to280° C. at a heating rate of 60° C. per hour and kept at 280° C. for 12hours. The reactor is cooled to 100° C., the nitrogen flow is turned offand the pressure is increased to 120 bar.

The catalyst is flushed with ammonia at 100° C., before the temperatureis increased to 184° C. and the alcohol feed is started with a WHSV of0.44 kg/liter*h (molar ratio ammonia/alcohol=27:1,hydrogen/alcohol=6:1). The crude material is collected and stripped on arotary evaporator to remove excess ammonia, light weight amines andreaction water to produce the aminated material. The analytical data ofthe reaction product is shown below.

Total Total Secondary Tertiary Primary amine- acetylatables and tertiaryamine- Hydroxyl Degree of Amine value value Value amine value valuevalue amination in % of total mg KOH/g mg KOH/g mg KOH/g mg KOH/g mgKOH/g in % amine 111.80 236.80 0.14 0.00 125.00 47.21 99.87

Example 5 Comparative Example 5b: 1 mol 2-butyl-2-ethyl-1,3-propandiol+4mol Propylene oxide+0.8 mol Acrylonitrile

In a 4-neck vessel with stirrer, thermometer, reflux condenser, nitrogeninlet, and dropping funnel, 392.1 g of product from example 2a isplaced. 4.7 g of a 50% aqueous solution of tetrakis (2-hydroxyethyl)ammonium hydroxide is added at room temperature. The mixture is heatedto 60° C. and 61.3 g acrylonitrile is added dropwise at 60° C. Afterstirring for 6 hours at given temperature, the mixture is stirred foradditional 14 hours at room temperature. The reaction product isfiltered and excess acrylonitrile is removed in vacuo. An orange liquidis obtained (414.0 g). Complete conversion of acrylonitrile is detectedby ¹H-NMR in CDCl₃. The degree of functionalization with acrylonitrileis detected by ¹H-NMR in CDCl₃ (peak at 2.6 ppm).

Comparative Example 5c: 1 mol 2-butyl-2-ethyl-1,3-propandiol+4 molPropylene oxide+0.8 mol Acrylonitrile, Hydrogenated

Product from 5b is hydrogenated over Raney cobalt in a continuouslyoperated autoclave. At a temperature of 110° C. and a pressure of 160bar, the nitrile (10 wt.-% in ethanol) is together with ammonia andhydrogen continuously fed into the reactor at such a rate that fullconversion of the nitrile is assured (controlled by NMR spectroscopy).The crude material is collected and stripped on a rotary evaporator toremove excess ammonia, light weight amines and ethanol to produce thehydrogenated material. The analytical data of the reaction product isshown below.

Total Total Secondary Tertiary Primary amine- acetylatables and tertiaryamine- Hydroxyl Degree of Amine value Value amine value value valueamination in % of total mg KOH/g mg KOH/g mg KOH/g mg KOH/g mg KOH/g in% amine 90.24 278.8 1.98 1.66 190.2 32.2 97.8

Example 6 Example 6b: 1 mol 2-butyl-2-ethyl-1,3-propandiol+4 molPropylene oxide+2 mol Acrylonitrile

In a 4-neck vessel with stirrer, thermometer, reflux condenser, nitrogeninlet, and dropping funnel, 39.3 g of product from example 2a is placed.0.23 g of a 50% aqueous solution of tetrakis (2-hydroxyethyl) ammoniumhydroxide is added at room temperature. The mixture is heated to 60° C.and 10.9 g acrylonitrile is added dropwise at 60° C. After stirring for1.5 hours at given temperature, the mixture is stirred for additional 14hours at room temperature. The reaction product is filtered and excessacrylonitrile is removed in vacuo. An orange liquid is obtained (36.5g). Complete conversion of acrylonitrile is detected by ¹H-NMR in CDCl₃.

Example 6c: 1 mol 2-butyl-2-ethyl-1,3-propandiol+4 mol Propylene oxide+2mol Acrylonitrile, Hydrogenated

Produce from example 6b is hydrogenated according to the representativeprocedure described in example 1c. The analytical data of the reactionproduct are shown below.

Total amine Secondary + tertiary Tertiary amine value amine value value[mg KOH/g] [mg KOH/g] [mg KOH/g] 204.70 1.21 1.09

Example 7 Example 7a: 1 mol 2-ethyl-1,3-hexane diol+4 mol PropyleneOxide

In a 2 l autoclave, 150.0 g 2-ethyl-1,3-hexane diol and 1.5 g potassiumhydroxide (50% aqueous solution) are mixed. The mixture is heated to110° C. and the water is removed in vacuo for 2 hours at 30 mbar. Theautoclave is purged three times with nitrogen and heated to 140° C.231.2 g propylene oxide is added within 2 hours. The mixture is allowedto post-react for 4 hours at 140° C. The reaction mixture is strippedwith nitrogen and volatile compounds are removed in vacuo at 80° C. Thecatalyst is removed by adding 11.4 g Macrosorb MP5plus, stirring at 100°C. for 2 hours and filtration. A yellowish oil is obtained (373.6 g,hydroxyl value: 245.0 mgKOH/g).

Example 7b: 1 mol 2-ethyl-1,3-hexane diol+4 mol Propylene oxide+2 molAcrylonitrile

In a 4-neck vessel with stirrer, thermometer, reflux condenser, nitrogeninlet, and dropping funnel, 151.3 g of product from example 7a isplaced. 3.6 g of a 50% aqueous solution of tetrakis (2-hydroxyethyl)ammonium hydroxide is added at room temperature. The mixture is heatedto 60° C. and 64.1 g acrylonitrile is added dropwise at 60° C. Afterstirring for 3 hours at given temperature, the mixture is stirred foradditional 14 hours at room temperature. The reaction product isfiltered and excess acrylonitrile is removed in vacuo. An orange liquidis obtained (174.0 g). Complete conversion of acrylonitrile is detectedby ¹H-NMR in CDCl₃. The degree of functionalization with acrylonitrileis detected by ¹H-NMR in CDCl3 (peak at 2.6 ppm).

Example 7c: 1 mol 2-ethyl-1,3-hexane diol+4 mol Propylene oxide+2 molAcrylonitrile, Hydrogenated

Product from example 7b is hydrogenated according to the representativeprocedure described in example 1c. The analytical data of the reactionproduct are shown below.

Total amine Secondary + tertiary Tertiary amine value amine value value[mg KOH/g] [mg KOH/g] [mg KOH/g] 218.7 5.76 1.02

Example 8 Example 8b: 1 mol 2-ethyl-1,3-hexane diol+4 mol Propyleneoxide+1.2 mol Acrylonitrile

In a 4-neck vessel with stirrer, thermometer, reflux condenser, nitrogeninlet, and dropping funnel, 151.3 g of product from example 7a isplaced. 4.8 g of a 50% aqueous solution of tetrakis (2-hydroxyethyl)ammonium hydroxide is added at room temperature. The mixture is heatedto 60° C. and 29.3 g acrylonitrile is added dropwise at 60° C. Afterstirring for 3 hours at given temperature, the mixture is stirred foradditional 14 hours at room temperature. The reaction product isfiltered and excess acrylonitrile is removed in vacuo. An orange liquidis obtained (160.0 g). Complete conversion of acrylonitrile is detectedby ¹H-NMR in CDCl₃. The degree of functionalization with acrylonitrileis detected by ¹H-NMR in CDCl₃ (peak at 2.6 ppm).

Example 8c: 1 mol 2-ethyl-1,3-hexane diol+4 mol Propylene oxide+1.2 molAcrylonitrile, Hydrogenated

Produce from example 8b is hydrogenated according to the representativeprocedure described in example 1c. The analytical data of the reactionproduct are shown below.

Total amine Secondary + tertiary Tertiary amine value amine value value[mg KOH/g] [mg KOH/g] [mg KOH/g] 146.9 4.52 0.82

Example 9 9a: Comparative Grease Stain Removal from Laundry DetergentCompositions

The following laundry detergent composition is prepared by traditionalmeans known to those of ordinary skill in the art by mixing the listedingredients.

TABLE 1 Detergent Composition DC1 percentage by Ingredients of liquiddetergent composition DC1 weight n-C10-C13-alkylbenzene sulfonic acid5.3 coconut C12-C18 fatty acid 2.4 sodium laureth sulfate + 2 EO 7.7potassium hydroxide 2.2 C13C15-oxo alcohol + 7 EO 5.4 1,2 propyleneglycol 6 Ethanol 2 Water to balance pH of detergent composition DC1 =8.4

Technical stain swatches of blue knitted cotton containing grease stainsare purchased from Warwick Equest Ltd. The stains are washed for 30 minin a launder-o-meter (manufactured by SDL Atlas) at room temperatureusing per canister 500 mL of washing solution, 20 steel balls (weight of1 ball is 1 g), and ballast fabrics. The washing solution contains 5000ppm of deter-gent composition DC1 (table 1). Water hardness is 2.5 mM(Ca2+:Mg2+ molar ratio was 4:1). Additives are added to the washingsolution of each canister separately and in the amount as detailedbelow. After addition, the pH value is readjusted to the pH value ofwashing solution without additive.

Standard colorimetric measurement is used to obtain L*, a* and b* valuesfor each stain before and after the washing. From L*, a* and b* values,the stain level is calculated as color difference AE (calculatedaccording to DIN EN ISO 11664-4) between stain and untreated fabric.

Stain removal from the swatches is calculated as follows:

${{Stain}\mspace{14mu}{Removal}\mspace{14mu}{Index}\mspace{14mu}({SRI})} = {\frac{\left( {{\Delta\; E_{initial}} - {\Delta\; E_{washed}}} \right)}{\Delta\; E_{initial}} \times 100}$

-   -   ΔE_(initial)=Stain level before washing    -   ΔE_(washed)=Stain level after washing

Stain level corresponds to the amount of grease on the fabric. The stainlevel of the fabric before the washing (ΔE_(initial)) is high; in thewashing process, stains are removed and the stain level after washing isreduced (ΔE_(washed)). The better a stain has been removed, the lesserthe value for ΔE_(washed) and the greater the difference betweenΔE_(initial) and ΔE_(washed) (ΔE_(initial)−ΔE_(washed)). Therefore, thevalue of the stain removal index increases with better washingperformance.

TABLE 2 Washing Test 1: SRI, stain: additive/[g] Beef Fat withoutadditive — 25.6 with Example 1c 0.0375 36.9 with Comparitive Example 3b0.0375 32.1 with Comparitive Example 5c 0.0375 29.5

TABLE 3 Washing Test 2: SRI, stain: Additive additive/[g] Chicken Fatwithout additive — 24.3 with Example 2c 0.0375 33.1 with ComparitiveExample 4b 0.0375 28.0

The washing tests with Examples 1 and 2 (Table 2 and Table 3) showimproved stain removal compared to Comparative Examples 3, 4, and 5.

9b: Anti-Redeposition Methodology and Data

The Anti-Redeposition Methodology uses a grease-soluble fluorescent dyeto mimic the redeposition behavior of grease. To summarize the method,the dye is incorporated in bacon grease and the fluorescent dye-dopedbacon grease is applied to fabrics to create a fluorescent grease stain.The fluorescent grease stain is incorporated into a wash system with aNIL-polymer detergent. The grease stains are washed for 12 mins. Thiscreates a suspension of fluorescent grease. Then the wash system ispaused and the etheramine is added to the wash system. The wash systemis stirred and clean white tracer fabrics are added to the wash systemand the wash is restarted. At the end of the wash, the tracers areremoved from the wash, dried, and evaluated to measure the fluorescentsignal on the tracer fabrics. The intensity of the fluorescent signal iscorrelated to the power of the etheramine to suspend greasy soils. Thelower the intensity of the fluorescent signal on the tracer fabric, thegreater the power of the etheramine for suspending grease.

To make stains with bacon grease doped with fluorescent dye start bydoping the fluorescent dye into bacon grease. The dye doped grease ismade at least one day before applying to fabric. To solubilize thefluorescent dye (Fluorol 555 CAS#19125-99-6, from Exciton Dayton, Ohio)into the grease, completely melt bacon grease (from EMC) in a 50° C.oven or water bath. Then add 0.1 g of Fluorol 555 to 100 g melted bacongrease and stir. This may be followed by sonication, to improve theuniformity of solubilization and reduce noise level of the method.

After at least one day, heat the bacon grease again in a 50° C. oven orwater bath until completely melted. Lay fabric swatches (cotton orpolycotton) out onto a weight cup to keep fabric suspended. Suspendingthe fabric over a cup, stops grease loss from bleeding through thefabric onto another surface, while the grease cools on the fabric. Witha 1 ml pipette apply three 250 ul spots (approximately 0.25 g) to 1cotton swatch spaced far enough to ensure the grease spots remainseparate and don't wick into each other. Applying three small stainsenables emulsification of the grease during the wash process. Keep thebacon grease fluid while applying, reintroduce into the oven or waterbath if the bacon grease begins to congeal to re-fluidize it. Let thestains rest over the weigh cup for several hours until these arethoroughly solidified. If stains will be stored for future use, thecooled stains can be layered with wax paper between the stains andwrapped in aluminum foil, then stored in the refrigerator. It isimportant to protect the stains from light and keep them cool to preventphoto-oxidation of the fluorescent dye and oxidation/microbialcontamination of the bacon grease. Stains can be stored in this mannerfor 1 month. Expired stains should be discarded.

TABLE 4 Detergent Composition DC2. Raw Material % C12-15 alkyl ethoxy(1.8) sulfate 11.27 Nonionic C24 EO9¹ 1.04 DTPA² 0.30 1,2 PropyleneGlycol 3.72 Monoethanolamine 3.17 Sodium Hydroxide 0.69 SodiumTetraborate 2.03 Alkyl benzene sulfonic acid 10.01 Sodium Formate 0.11Citric Acid 2.87 C1218 Fatty Acid 1.11 Calcium Formate 0.10 Ethanol 1.49Water Balance to 100% ¹Nonionic 24-9 is a C12-14 alcohol ethoxylate,with an average degree of ethoxylation of 9. ²DTPA isdiethylenetetraamine pentaacetic acid.

To create the wash suspension of fluorescent dye-doped grease, startwith a 5.29 g of a detergent containing surfactant and NIL-polymer(detergent composition DC2 of Table 4). Add two soiled fabrics with 3spots each of dyed grease (approximately 1.5 g of fluorescent dye-dopedgrease) in 7.5 L of water in a mini-washer washing machine tub. Add 200g of clean terry ballast. Set wash conditions at 30.5° C., 119.7 ppm ofa 3:1 Ca²⁺/Mg²⁺ (0.98 moles Ca^(2+/)) mix to simulate water hardness.

After 12 min., remove the dyed grease stains and add three polycotton50/50 tracers and polyetheramine and agitate for 30 s. After agitation,complete another 12 min. wash cycle and 2 min. rinse (70° F.). Dry eachtest load plus ballast (in separate dryers) for 50 min (normal dryercycle). To improve signal sensitivity, run the test swatches through 2more cycles w/the etheramine to create 3 cycles of deposition of dyedgrease.

Cut samples from the traces to fit into a 12-24 well plate. Place cutsamples in the bottom of the well and use o-rings to hold the swatchesflat in the well. Read 3-6 spots per treatment. Sample the most uniform,representative parts of the tracer swatch. Read the fluorescenceintensity on the samples using a reflectance fluorescence spectrometer(BMG Fluostar).

Index the test samples to the control samples (NIL-polymer detergent)equation: (test signal−control signal)/control signal=index. If theindex is a negative number, the test sample provides improvedanti-redeposition versus the control. If the test sample is positive, itis causing increased deposition versus control.

Comparative example 9 is prepared by a process similar to the onedescribed for comparative example 4b but conditions are adapted toobtain a higher degree of amination.

TABLE 5 Anti- redeposition Molecule Name Molecular Structure IndexComparative example 9

−14.75 Example lc (2-Butyl-2-Ethyl- Propanediol) (PO/OH)1 (CAN/)H)1hydrogenated

−17.14 Example 6c (2-Butyl-2-Ethyl- Propanediol) (PO/OH)2 (CAN/)H)1hydrogenated

−19.88

The index is more negative for examples 1c and 6c, as compared toComparative example 9. Examples 1c and 6c provide improvedanti-redeposition versus Comparative example 9.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm”.

Every document cited herein, including any cross referenced or relatedpatent or application, is hereby incorporated herein by reference in itsentirety unless expressly excluded or otherwise limited. The citation ofany document is not an admission that it is prior art with respect toany invention disclosed or claimed herein or that it alone, or in anycombination with any other reference or references, teaches, suggests ordiscloses any such invention. Further, to the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.”

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A method of forming an etheramine: the methodcomprising reductive cyanoethylation of an alkoxylated 1,3-diol mixturewith an acrylonitrile in the presence of a base followed byhydrogentation with hydrogen and a catalyst to form an etheramine ofFormula (I), Formula (II), or a mixture thereof:

wherein each of R₁-R₁₂ is independently selected from H, alkyl,cycloalkyl, aryl, alkylaryl, or arylalkyl, wherein at least one of R₁-R₆and at least one of R₇-R₁₂ is different from H, each of A₁-A₉ isindependently selected from linear or branched alkanediyl groups having2 to 18 carbon atoms, wherein each of Z₁-Z₄ is independently selectedfrom —OH and linear —OCH₂CH₂CH₂NH₂, wherein the degree of amination ofeach of the etheramines of Formula (I) and Formula (II) is equal to orgreater than 50%, wherein the sum of x+y is in the range of about 2 toabout 200, wherein x≥1 and y≥1, and the sum of x₁+y₁ is in the range ofabout 2 to about
 200. 2. The method of claim 1, wherein the etheramineof Formula (I), Formula (II), or a mixture thereof comprises an A₁-A₉that is independently selected from linear or branched alkanediyl groupshaving 2-10 carbon atoms, most preferably 2-5 carbon atoms.
 3. Themethod of claim 1, wherein the etheramine of Formula (I), Formula (II),or a mixture thereof comprises an A₁-A₉ that is independently selectedfrom linear or branched alkanediyl groups having 2-5 carbon atoms. 4.The method of claim 1, wherein the etheramine of Formula (I), Formula(II), or a mixture thereof comprises a sum of x+y is in the range ofabout 2 to about
 20. 5. The method of claim 1, wherein the etheramine ofFormula (I), Formula (II), or a mixture thereof comprises a sum of x₁+y₁is in the range of about 2 to about
 20. 6. The method of claim 1,wherein the etheramine of Formula (I), Formula (II), or a mixturethereof comprises an A₁-A₉ that is independently selected from linear orbranched alkanediyl groups having 2-5 carbon atoms, wherein the sum ofx+y is in the range of about about 2 to about 10, and wherein the sum ofx₁+y₁ is in the range of about 2 to about 10, wherein x₁≥1 and y₁≥1. 7.The method of claim 1, wherein the etheramine of Formula (I), Formula(II), or a mixture thereof comprises a degree of amination of saidetheramine of Formula (I) and/or Formula (II) is equal to or greaterthan about 55%.
 8. The method of claim 1, wherein in said etheramine ofFormula (I) or Formula (II), x+y is in the range of about 2 to about 8and x₁+y₁ is in the range of about 2 to about
 8. 9. The method of claim1, wherein the etheramine of Formula (I), Formula (II), or a mixturethereof comprises an etheramine mixture comprising at least 95%, morepreferably at least 90%, by weight of said etheramine mixture, of saidetheramine of Formula (I), said etheramine of Formula(II), or a mixturethereof.
 10. The method of claim 1, wherein in said etheramine ofFormula (I) or Formula (II), each of A₁-A₉ is independently selectedfrom the group consisting of ethylene, propylene, butylene, and mixturesthereof, preferably each of A₁-A₉ is propylene.
 11. The method of claim1, wherein in said etheramine of Formula (I) or Formula (II), each ofR₁, R₂, R₅, R₆, R₇, R₈, R₁₁, and R₁₂ is H and each of R₃, R₄, R₉, andR₁₀ is independently selected from C1-C16 alkyl or aryl, preferably eachof R₃, R₄, R₉, and R₁₀ is independently selected from a butyl group, anethyl group, a methyl group, a propyl group, or a phenyl group.
 12. Themethod of claim 1, wherein in said etheramine of Formula (I) or Formula(II), each of R₃ and R₉ is an ethyl group, each of R₄ and R₁₀ is a butylgroup, and each of R₁, R₂, R₅, R₆, R₇, R₈, R₁₁, and R₁₂ is H.
 13. Themethod of claim 1, wherein in said etheramine of Formula (I) or Formula(II), each of R₁, R₂, R₇, and R₈ is H and each of R₃, R₄, R₅, R₆, R₉,R₁₀, R₁₁, and R₁₂ is independently selected from an ethyl group, amethyl group, a propyl group, a butyl group, a phenyl group, or H. 14.The method of claim 1, wherein said etheramine has a weight averagemolecular weight of about 290 to about 1000 grams/mole.
 15. The methodof claim 1, wherein said etheramine has a weight average molecularweight of about 290 to about 900 grams/mole.
 16. The method of claim 1,wherein said etheramine has a weight average molecular weight of about300 to about 450 grams/mole.
 17. The method of claim 1, wherein the basecomprises alkaline hydroxides and substituted ammonium hydroxide. 18.The method of claim 1, wherein the catalyst for hydrogenation of thenitrile function to the corresponding amine comprises one or more of Fe,Co, Ni, Ru, Rh, Pd, Os, Ir, or Pt.